Process for producing vinyl polymer

ABSTRACT

The present invention provides a method for producing a vinyl polymer including the steps of polymerizing a vinyl monomer by atom transfer radical polymerization with a transition metal complex as a polymerization catalyst, and bringing the resultant vinyl polymer into contact with an adsorbent in the presence of an oxidizing agent; the vinyl polymer produced by the method; and a reactive composition susceptible to hydrosilylation containing the vinyl polymer produced by the method and having at least one alkenyl group per molecule.

This application is a 371 national phase application of PCT/JP02/10775filed on 17 Oct. 2002, claiming priority to JP 2001-318941, filed on 17Oct. 2001, and JP 2001-339039 filed 05 Nov. 2001, the contents of whichare incorporated herein by reference in their entirety.

TECHNICAL FIELD

The present invention relates to a method for producing a vinyl polymer,the vinyl polymer, and a reactive composition susceptible tohydrosilylation.

BACKGROUND ART

Hydrosilylation is one of the most industrially useful reactions, and isused in, for example, functional group conversion and crosslinkingreactions. For example, polymers having alkenyl functional groups at theends of the molecular chains are cured by crosslinking using compoundshaving hydrosilyl groups as a curing agent. The resultant curedmaterials have superior heat resistance and durability. Furthermore,polymers having alkenyl groups at the ends of the molecular chains arereacted with compounds including hydrosilyl groups having crosslinkablesilyl groups to produce polymers having the crosslinkable silyl groupsat the ends of the polymers. Although these hydrosilylation reactionsproceed by heating, a hydrosilylation catalyst is added in order topromote the reaction. The hydrosilylation catalysts include a radicalinitiator such as organic peroxides and azo compounds, and transitionmetal catalysts. In particular, it is known that transition metalcatalysts can promote the hydrosilylation depending on the catalystcontent.

On the other hand, living polymerization is generally known as asynthetic method that can synthesize polymers accurately. The livingpolymerization can not only readily control molecular weights andmolecular weight distributions, but also produce polymers whose endstructures are definite. Accordingly, the living polymerization is oneof the useful methods to introduce functional groups to the ends of thepolymers. Recently, some radical polymerization systems in which theliving polymerization can also proceed have been found, and livingradical polymerization has been studied extensively. In particular, atomtransfer radical polymerization yields vinyl polymers having a smallmolecular weight distribution. In the atom transfer radicalpolymerization system, examples of the initiator include halogenatedorganic compounds or sulfonyl halides, and the catalysts include metalcomplexes containing an element in group 8, group 9, group 10, or group11 in the periodic table, the element being contained as a centralmetal. (For example, see Matyjaszewski et al. J. Am. Chem. Soc. 1995,vol. 117, p. 5614, Macromolecules 1995, vol. 28, p. 7901, Science 1996,vol. 272, p. 866, and Sawamoto et al. Macromolecules 1995, vol. 28, p.1721.)

However, since a transition metal complex used as the polymerizationcatalyst remains in the vinyl polymer produced by the atom transferradical polymerization, the above methods cause problems of the coloringof the polymer and environmental safety, and influence the physicalproperty of the polymer. Unfortunately, for example, in vinyl polymershaving terminal alkenyl groups produced by the atom transfer radicalpolymerization, residual catalysts function as anticatalysts of thehydrosilylation reaction. Therefore, the residual catalysts inhibit thehydrosilylation, and a large amount of expensive hydrosilylationcatalyst is necessary.

According to Japanese Unexamined Patent Application Publication No.11-193307, a vinyl polymer produced by the atom transfer radicalpolymerization is purified by bringing the vinyl polymer into contactwith an adsorbent such as aluminum silicate, thereby improving thehydrosilylation activity of the vinyl polymer. However, the improvementin the hydrosilylation activity is not sufficient with respect to thecontent of the adsorbent. In order to achieve sufficient hydrosilylationactivity, the process requires a large amount of adsorbent.Unfortunately, the waste causes a high level of environmental load, andthe use of the adsorbent causes an increase in purification cost.

SUMMARY OF THE INVENTION

In order to solve the above problems, it is an object of the presentinvention to provide a simple, economical, and efficient method forimproving the hydrosilylation activity of a vinyl polymer withmaintaining the original properties of the vinyl polymer.

The present invention provides a method for producing a vinyl polymerincluding the steps of polymerizing a vinyl monomer by atom transferradical polymerization with a transition metal complex as apolymerization catalyst, and bringing the resultant vinyl polymer intocontact with an adsorbent in the presence of an oxidizing agent.

The present invention also provides the vinyl polymer produced by theabove method.

Furthermore, the present invention provides a reactive compositionsusceptible to hydrosilylation containing the vinyl polymer produced bythe above method and having at least one alkenyl group per molecule.

The present invention will now be described in detail.

DISCLOSURE OF INVENTION

The process for producing a vinyl polymer will now be described.

According to the method of the present invention, a vinyl monomer ispolymerized by atom transfer radical polymerization with a transitionmetal complex as a polymerization catalyst to produce a vinyl polymer.

Atom Transfer Radical Polymerization

The atom transfer radical polymerization will now be described indetail. The atom transfer radical polymerization in the presentinvention is a kind of living radical polymerization. According to theatom transfer radical polymerization, a vinyl monomer is polymerized byradical polymerization using a halogenated organic compound or asulfonyl halide as an initiator and a metal complex containing atransition metal as a central metal as a catalyst. Examples of thepolymerization are disclosed by Matyjaszewski et al. [Journal ofAmerican Chemical Society (J. Am. Chem. Soc.) 1995, vol. 117, p. 5614;Macromolecules 1995, vol. 28, p. 7901; Science 1996, vol. 272, p. 866;PCT Publication Nos. WO96/30421, WO97/18247, WO98/01480, andWO98/40415]; and by Sawamoto et al. [Macromolecules 1995, vol. 28, p.1721; and Japanese Unexamined Patent Application Publication Nos.9-208616 and 8-41117].

Examples of the initiator used in the atom transfer radicalpolymerization include halogenated organic compounds, in particular,halogenated organic compounds having a highly reactive carbon-halogenbond (for example, carbonyl compounds having a halogen atom at theα-position and compounds having a halogen atom at the benzylic position)or sulfonyl halides. Examples of the initiator include

-   C₆H₅—CH₂X,-   C₆H₅—C(H)(X)CH₃, and-   C₆H₅—C(X)(CH₃)₂,    (wherein C₆H₅ represents a phenyl group and X represents a chlorine    atom, a bromine atom, or an iodine atom); and-   R³—C(H)(X)—CO₂R⁴,-   R³—C(CH₃)(X)—CO₂R⁴,-   R³—C(H)(X)—C(O)R⁴,-   R³—C(CH₃)(X)—C(O)R⁴, and-   R³—C₆H₄—SO₂X    (wherein R³ and R⁴ independently represent a hydrogen atom, an alkyl    group of 1 to 20 carbon atoms, an aryl group of 1 to 20 carbon    atoms, or an aralkyl group of 1 to 20 carbon atoms, and X represents    a chlorine atom, a bromine atom or an iodine atom).

A vinyl monomer is polymerized by atom transfer radical polymerizationusing a halogenated organic compound or a sulfonyl halide as aninitiator to produce a vinyl polymer having an end structure representedby general formula (1):—C(R¹)(R²)(X)  (1)(wherein R¹ and R² represent a group bonded to an ethylenicallyunsaturated group of the vinyl monomer, and X represents a chlorineatom, a bromine atom, or an iodine atom).

Halogenated organic compounds or sulfonyl halides having both afunctional group that initiate the polymerization and a specificreactive functional group that does not initiate the polymerization maybe used as the initiator for the atom transfer radical polymerization.In this case, the resultant vinyl polymer has the specific reactivefunctional group at one end of the main chain, and has the end structurerepresented by general formula (1) at the other end of the main chain.Examples of the specific reactive functional group include alkenyl,crosslinkable silyl, hydroxyl, epoxy, amino, and amido groups. Otherfunctional groups can be introduced in the vinyl polymer by utilizingthe reactivity of these reactive functional groups, through one orseveral reaction steps.

The halogenated organic compound having an alkenyl group is not limitedand includes, for example, a compound represented by general formula(2):R⁶R⁷C(X)—R⁸—R⁹—C(R⁵)═CH²  (2)(wherein R⁵ represents a hydrogen atom or a methyl group; each of R⁶ andR⁷ represents a hydrogen atom, a monovalent alkyl group of 1 to 20carbon atoms, an aryl group of 1 to 20 carbon atoms, an aralkyl group of1 to 20 carbon atoms, or a group that forms a cyclic structure bybonding each other at their ends; R⁸ represents —C(O)O— (an estergroup), —C(O)— (a keto group), or an o-, m-, p-phenylene group; R⁹represents a direct bond, or a divalent organic group of 1 to 20 carbonatoms, the divalent organic group may include at least one ether bond;and X represents a chlorine atom, a bromine atom, or an iodine atom).

Examples of the substituents R⁶ and R⁷ include a hydrogen atom, methylgroup, ethyl group, n-propyl group, iso-propyl group, butyl group,pentyl group, and hexyl group. R⁶ and R⁷ may bond to each other at theirends to form a cyclic structure.

Examples of the halogenated organic compound represented by generalformula (2), the halogenated organic compound having an alkenyl groupinclude

-   XCH₂C(O)O(CH₂)_(n)CH═CH₂,-   H₃CC(H)(X)C(O)O(CH₂)_(n)CH═CH₂,-   (H₃C)₂C(X)C(O)O(CH₂)_(n)CH═CH₂,-   CH₃CH₂C(H)(X)C(O)O(CH₂)_(n)CH═CH₂, and

(wherein X represents a chlorine atom, a bromine atom, or an iodineatom, and n represents an integer of 0 to 20);

-   XCH₂C(O)O(CH₂)_(n)O(CH₂)_(m)CH═CH₂,-   H₃CC(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)CH═CH₂,-   (H₃C)₂C(X)C(O)O(CH₂)_(n)O(CH₂)_(m)CH═CH₂,-   CH₃CH₂C(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)CH═CH₂, and

(wherein X represents a chlorine atom, a bromine atom, or an iodineatom, n represents an integer of 0 to 20, and m represents an integer of0 to 20);

-   o, m, p-XCH₂—C₆H₄—(CH₂)_(n)—CH═CH₂,-   o, m, p-CH₃C(H)(X)—C₆H₄—(CH₂)_(n)—CH═CH₂, and-   o, m, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)_(n)—CH═CH₂,    (wherein X represents a chlorine atom, a bromine atom, or an iodine    atom, and n represents an integer of 0 to 20);-   o, m, p-XCH₂—C₆H₄—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂,-   o, m, p-CH₃C(H)(X)—C₆H₄—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂, and-   o, m, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂,    (wherein X represents a chlorine atom, a bromine atom, or an iodine    atom, n represents an integer of 0 to 20, and m represents an    integer of 0 to 20);-   o, m, p-XCH₂—C₆H₄—O—(CH₂)_(n)—CH═CH₂,-   o, m, p-CH₃C(H)(X)—C₆H₄—O—(CH₂)_(n)—CH═CH₂, and-   o, m, p-CH₃CH₂C(H)(X)—C₆H₄—O—(CH₂)_(n)—CH═CH₂,    (wherein X represents a chlorine atom, a bromine atom, or an iodine    atom and n represents an integer of 0 to 20); and-   o, m, p-XCH₂—C₆H₄—O—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂,-   o, m, p-CH₃C(H)(X)—C₆H₄—O—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂, and-   o, m, p-CH₃CH₂C(H)(X)—C₆H₄—O—(CH₂)_(n)—O—(CH₂)_(m)—CH═CH₂,    (wherein X represents a chlorine atom, a bromine atom, or an iodine    atom, n represents an integer of 0 to 20, and m represents an    integer of 0 to 20).

Examples of the halogenated organic compound having an alkenyl groupfurther include compounds represented by general formula (3):H₂C═C(R⁵)—R⁹—C(R⁶)(X)—R¹⁰—R⁷  (3)(wherein R⁵, R⁶, R⁷, R⁹, and X are as defined above, R¹⁰ represents adirect bond, C(O)O— (an ester group), —C(O)— (a keto group), or an o-,m-, p-phenylene group).

R⁸ represents a direct bond or a divalent organic group of 1 to 20carbon atoms (the divalent organic group may include at least one etherbond). When R⁸ is a direct bond, a vinyl group is bonded to a carbonthat is bonded to a halogen. That is, the compound is an allyl halide.In this case, the bond between the carbon and the halogen is activatedby the adjacent vinyl group. Therefore, R¹⁰ is not always a C(O)O groupor a phenylene group, and may be a direct bond. When R⁹ is not a directbond, R¹⁰ is preferably a C(O)O group, a C(O) group, or a phenylenegroup in order to activate the bond between the carbon and the halogen.

Examples of the compound represented by general formula (3) include

-   CH₂═CHCH₂X,-   CH₂═C(CH₃)CH₂X,-   CH₂═CHC(H)(X)CH₃, CH₂═C(CH₃)C(H)(X)CH₃,-   CH₂═CHC(X)(CH₃)₂, CH₂═CHC(H)(X)C₂H₅,-   CH₂═CHC(H)(X)CH(CH₃)₂,-   CH₂═CHC(H)(X)C₆H₅, CH₂═CHC(H)(X)CH₂C₆H₅,-   CH₂═CHCH₂C(H)(X)—CO₂R,-   CH₂═CH(CH₂)₂C(H)(X)—CO₂R,-   CH₂═CH(CH₂)₃C(H)(X)—CO₂R,-   CH₂═CH(CH₂)₈C(H)(X)—CO₂R,-   CH₂═CHCH₂C(H)(X)—C₆H₅,-   CH₂═CH(CH₂)₂C(H)(X)—C₆H₅, and-   CH₂═CH(CH₂)₃C(H)(X)—C₆H₅,    (wherein X represents a chlorine atom, a bromine atom or an iodine    atom, R represents an alkyl group of 1 to 20 carbon atoms, an aryl    group of 1 to 20 carbon atoms, or an aralkyl group of 1 to 20 carbon    atoms).

Examples of the sulfonyl halide having an alkenyl group include

-   -   o-, m-, p-CH₂═CH—(CH₂)_(n)—C₆H₄—SO₂X, and    -   o-, m-, p-CH₂═CH—(CH₂)_(n)—O—C₆H₄—SO₂X,        (wherein X represents a chlorine atom, a bromine atom, or an        iodine atom, and n represents an integer of 0 to 20).

The halogenated organic compound having a crosslinkable silyl group isnot limited. Examples of the compound include the compound representedby general formula (4):R⁶R⁷C(X)—R⁸—R⁹—C(H)(R⁵)CH₂—[(Si(R¹¹)_(2-b)(Y)_(b)O]_(m)—Si(R¹²)_(3-a)(Y)_(a)  (4)(wherein R⁵, R⁶, R⁷, R⁸, R⁹, and X are as defined above; each of R¹¹ andR¹² represents an alkyl group of 1 to 20 carbon atoms, an aryl group of1 to 20 carbon atoms, or an aralkyl group of 1 to 20 carbon atoms or atriorganosiloxy group represented by (R′)₃SiO— (wherein R′ represents amonovalent hydrocarbon group of 1 to 20 carbon atoms and the three R′smay be the same or different); when the number of R¹¹s or R¹²s is two ormore, each of the R¹¹ or R¹² may be the same or different; Y representsa hydroxyl group or a hydrolyzable group; when the number of Ys is twoor more, each of Y may be the same or different; a represents 0, 1, 2,or 3, b represents 0, 1, or 2, and m represents an integer of 0 to 19,wherein a+mb≧1).

Examples of the compounds represented by general formula (4) include

-   XCH₂C(O)O(CH₂)_(n)Si(OCH₃)₃,-   CH₃C(H)(X)C(O)O(CH₂)_(n)Si(OCH₃)₃,-   (CH₃)₂C(X)C(O)O(CH₂)_(n)Si(OCH₃)₃,-   XCH₂C(O)O(CH₂)_(n)Si(CH₃)(OCH₃)₂,-   CH₃C(H)(X)C(O)O(CH₂)_(n)Si(CH₃)(OCH₃)₂, and-   (CH₃)₂C(X)C(O)O(CH₂)_(n)Si(CH₃)(OCH₃)₂,    (wherein X represents a chlorine atom, a bromine atom, or an iodine    atom and n represents an integer of 0 to 20);-   XCH₂C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,-   H₃CC(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,-   (H₃C)₂C(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,-   CH₃CH₂C(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)Si(OCH₃)₃,-   XCH₂C(O)O(CH₂)_(n)O(CH₂)_(m)Si(CH₃)(OCH₃)₂,-   H₃CC(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)—Si(CH₃)(OCH₃)₂,-   (H₃C)₂C(X)C(O)O(CH₂)_(n)O(CH₂)_(m)—Si(CH₃)(OCH₃)₂, and-   CH₃CH₂C(H)(X)C(O)O(CH₂)_(n)O(CH₂)_(m)—Si(CH₃)(OCH₃)₂,    (wherein X represents a chlorine atom, a bromine atom, or an iodine    atom, n represents an integer of 0 to 20, and m represents an    integer of 0 to 20); and-   o, m, p-XCH₂—C₆H₄—(CH₂)₂Si(OCH₃)₃,-   o, m, p-CH₃C(H)(X)—C₆H₄—(CH₂)₂Si(OCH₃)₃,-   o, m, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)₂Si(OCH₃)₃,-   o, m, p-XCH₂—C₆H₄—(CH₂)₃Si(OCH₃)₃,-   o, m, p-CH₃C(H)(X)—C₆H₄—(CH₂)₃Si(OCH₃)₃,-   o, m, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)₃Si(OCH₃)₃,-   o, m, p-XCH₂—C₆H₄—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,-   o, m, p-CH₃C(H)(X)—C₆H₄—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,-   o, m, p-CH₃CH₂C(H)(X)—C₆H₄—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,-   o, m, p-XCH₂—C₆H₄—O—(CH₂)₃Si(OCH₃)₃,-   o, m, p-CH₃C(H)(X)—C₆H₄—O—(CH₂)₃Si(OCH₃)₃,-   o, m, p-CH₃CH₂C(H)(X)—C₆H₄—O—(CH₂)₃—Si(OCH₃)₃,-   o, m, p-XCH₂—C₆H₄—O—(CH₂)₂—O—(CH₂)₃—Si(OCH₃)₃,-   o, m, p-CH₃C(H)(X)—C₆H₄—O—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃, and-   o, m, p-CH₃CH₂C(H)(X)—C₆H₄—O—(CH₂)₂—O—(CH₂)₃Si(OCH₃)₃,    (wherein X represents a chlorine atom, a bromine atom, or an iodine    atom).

The halogenated organic compound having a crosslinkable silyl groupfurther includes the compound represented by general formula (5):(R¹²)_(3-a)(Y)_(a)Si—[OSi(R¹¹)_(2-b)(Y)_(b)]_(m)—CH₂—C(H)(R⁵)—R⁹—C(R⁶)(X)—R¹⁰—R⁷  (5)(wherein R⁵, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², a, b, m, X, and Y are as definedabove).

Examples of the compound include

-   (CH₃O)₃SiCH₂CH₂C(H)(X)C₆H₅,-   (CH₃O)₂(CH₃)SiCH₂CH₂C(H)(X)C₆H₅,-   (CH₃O)₃Si(CH₂)₂C(H)(X)—CO₂R,-   (CH₃O)₂(CH₃)Si(CH₂)₂C(H)(X)—CO₂R,-   (CH₃O)₃Si(CH₂)₃C(H)(X)—CO₂R,-   (CH₃O)₂(CH₃)Si(CH₂)₃C(H)(X)—CO₂R,-   (CH₃O)₃Si(CH₂)₄C(H)(X)—CO₂R,-   (CH₃O)₂(CH₃)Si(CH₂)₄C(H)(X)—CO₂R,-   (CH₃O)₃Si(CH₂)₉C(H)(X)—CO₂R,-   (CH₃O)₂(CH₃)Si(CH₂)₉C(H)(X)—CO₂R,-   (CH₃O)₃Si(CH₂)₃C(H)(X)—C₆H₅,-   (CH₃O)₂(CH₃)Si(CH₂)₃C(H)(X)—C₆H₅,-   (CH₃O)₃Si(CH₂)₄C(H)(X)—C₆H₅, and-   (CH₃O)₂(CH₃)Si(CH₂)₄C(H)(X)—C₆H₅,    (wherein X represents a chlorine atom, a bromine atom or an iodine    atom, R represents an alkyl group of 1 to 20 carbon atoms, an aryl    group of 1 to 20 carbon atoms, or an aralkyl group of 1 to 20 carbon    atoms).

The halogenated organic compound having a hydroxyl group or the sulfonylhalide having a hydroxyl group is not limited. Examples of the compoundinclude:

-   HO—(CH₂)_(n)—OC(O)C(H)(R)(X)    (wherein X represents a chlorine atom, a bromine atom, or an iodine    atom, R represents a hydrogen atom, an alkyl group of 1 to 20 carbon    atoms, an aryl group of 1 to 20 carbon atoms, or an aralkyl group of    1 to 20 carbon atoms, and n represents an integer of 0 to 20).

The halogenated organic compound having an amino group or the sulfonylhalide having an amino group is not limited. Examples of the compoundinclude:

-   H₂N—(CH₂)_(n)—OC(O)C(H)(R)(X)    (wherein X represents a chlorine atom, a bromine atom, or an iodine    atom, R represents a hydrogen atom, an alkyl group of 1 to 20 carbon    atoms, an aryl group of 1 to 20 carbon atoms, or an aralkyl group of    1 to 20 carbon atoms, and n represents an integer of 0 to 20).

The halogenated organic compound having an epoxy group or the sulfonylhalide having an epoxy group is not limited. Examples of the compoundinclude:

(wherein X represents a chlorine atom, a bromine atom, or an iodineatom, R represents a hydrogen atom, an alkyl group of 1 to 20 carbonatoms, an aryl group of 1 to 20 carbon atoms, or an aralkyl group of 1to 20 carbon atoms, and n represents an integer of 0 to 20).

In order to produce a polymer having two or more reactive functionalgroups per molecule, the initiator is preferably a halogenated organiccompound or a sulfonyl halide having two or more initiation points.Examples of the compound include:

(wherein C₆H₄ represents a phenylene group and X represents a chlorineatom, a bromine atom, or an iodine atom);

(wherein R represents an alkyl group of 1 to 20 carbon atoms, an arylgroup of 1 to 20 carbon atoms, or an aralkyl group of 1 to 20 carbonatoms, n represents an integer of 0 to 20, and X represents a chlorineatom, a bromine atom, or an iodine atom);

(wherein, X represents a chlorine atom, a bromine atom, or an iodineatom and n represents an integer of 0 to 20);

(wherein, n represents an integer of 0 to 20 and X represents a chlorineatom, a bromine atom, or an iodine atom); and

(wherein, X represents a chlorine atom, a bromine atom, or an iodineatom).

Although the transition metal complex used as the polymerizationcatalyst is not limited, the transition metal complex preferablyincludes a metal complex containing an element in group 7, group 8,group 9, group 10, or group 11 in the periodic table, the element beingcontained as a central metal. More preferably, the transition metalcomplex includes a complex of zero-valent copper, monovalent copper,divalent ruthenium, divalent iron, or divalent nickel. In particular, acopper complex is preferable. Examples of the monovalent copper compoundinclude cuprous chloride, cuprous bromide, cuprous iodide, cuprouscyanide, cuprous oxide, and cuprous perchlorate. When the coppercompounds are used, a ligand, for example, 2,2′-bipyridyl or itsderivative, 1,10-phenanthroline or its derivative, or a polyamine suchas diamine, e.g. tetramethylethylenediamine, a triamine, e.g.pentamethyldiethylenetriamine, or hexamethyl tris (2-aminoethyl) amineis added in order to enhance the catalytic activity. Tristriphenylphosphine complex containing divalent ruthenium chloride(RuCl₂(PPh₃)₃) is also preferable as the catalyst. When rutheniumcompounds are used as the catalyst, aluminum alkoxides are added as anactivating agent. Furthermore, bis triphenylphosphine complex containingdivalent iron (FeCl₂(PPh₃)₂), bis triphenylphosphine complex containingdivalent nickel (NiCl₂(PPh₃)₂), and bis tributylphosphine complexcontaining divalent nickel (NiBr₂(PBu₃)₂) are also preferable as thecatalyst.

The vinyl monomer used in this polymerization is not limited. Examplesof the vinyl monomer include (meth)acrylic monomers such as(meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate,n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl(meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate,n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl(meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate,2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate,dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate,benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl(meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate,2-aminoethyl (meth)acrylate, γ-(methacryloyl oxypropyl) trimethoxysilane, (meth)acrylic acid ethylene oxide adducts, trifluoromethylmethyl(meth)acrylate, 2-trifluoromethylethyl (meth)acrylate,2-perfluoroethylethyl (meth)acrylate,2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, 2-perfluoroethyl(meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl(meth)acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate,2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl(meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate; styrenicmonomers such as styrene, vinyltoluene, α-methyl styrene, chlorostyrene,styrenesulfonic acid, and salts thereof; fluorine-containing vinylmonomers such as perfluoroethylene, perfluoropropylene, and vinylidenefluoride; silicon-containing vinyl monomers such asvinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleicacid, monoalkyl maleate, and dialkyl maleate; fumaric acid, monoalkylfumarate, and dialkyl fumarate; maleimide monomers such as maleimide,methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide,hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide,phenylmaleimide, and cyclohexylmaleimide; nitrile group-containing vinylmonomers such as acrylonitrile and methacrylonitrile; amidogroup-containing vinyl monomers such as acrylamide and methacrylamide;vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate,vinyl benzoate, and vinyl cinnamate; alkenes such as ethylene andpropylene; conjugated dienes such as butadiene and isoprene; vinylchloride, vinylidene chloride, allyl chloride, and allyl alcohol. Thesemonomers may be used alone or used in combination to copolymerize. Interms of the physical properties of the product, the styrene monomersand the (meth)acrylic monomers are preferably used. In particular,acrylate monomers and methacrylate monomers are preferably used, morepreferably, acrylate monomers are used, and most preferably, butylacrylate is used. According to the present invention, the preferablemonomers may be copolymerized, furthermore, may be subjected to blockcopolymerization with other monomers. In this case, the content of thepreferable monomers is preferably 40 percent by weight. In the aboveexpression, for example, (meth)acrylic acid represents acrylic acidand/or methacrylic acid.

The polymerization reaction may be performed in a solvent-free system orin various solvents. The kind of the solvent is not limited. Examples ofthe solvent include hydrocarbons such as benzene and toluene; etherssuch as diethyl ether, tetrahydrofuran, diphenyl ether, anisole, anddimethoxybenzene; halogenated hydrocarbons, such as methylene chloride,chloroform, and chlorobenzene; ketones such as acetone, methyl ethylketone, and methyl isobutyl ketone; alcohols such as methanol, ethanol,propanol, isopropyl alcohol, n-butyl alcohol, and tert-butyl alcohol;nitrites such as acetonitrile, propionitrile, and benzonitrile; esterssuch as ethyl acetate and butyl acetate; carbonates such as ethylenecarbonate and propylene carbonate; and amides such asN,N-dimethylformamide and N,N-dimethylacetamide. These solvents may beused alone or in combination. Furthermore, the polymerization may beperformed in an emulsion system or in a system using a supercriticalfluid CO₂ as a medium.

Although the temperature during the polymerization is not limited, thepolymerization is generally performed in the range of 0° C. to 200° C.,and preferably in the range of room temperature to 150° C.

Vinyl Polymer

The vinyl polymer according to the present invention will now bedescribed in detail.

The molecular weight distribution of the vinyl polymer, i.e., the ratioof the weight average molecular weight to the number average molecularweight measured by gel permeation chromatography (GPC), is not limited.The molecular weight distribution of the vinyl polymer is generally lessthan 1.8, preferably less than 1.7, more preferably less than 1.6, inparticular, less than 1.5, still more preferably less than 1.4, and mostpreferably less than 1.3. According to the GPC in the present invention,generally, chloroform is used as a mobile phase, and a polystyrene gelcolumn is used for the measurement. For example, the number averagemolecular weight can be determined with a polystyrene standard.

Although the number average molecular weight of the vinyl polymer is notlimited, the number average molecular weight is preferably in the rangeof 500 to 1,000,000, more preferably, 1,000 to 100,000. A significantlylow molecular weight does not exhibit the original properties of thevinyl polymer, whereas a significantly high molecular weight precludesthe handling.

The vinyl polymer may have a reactive functional group in the molecule.The vinyl polymer may have the reactive functional group either at aside chain or an end of the molecular chain. The reactive functionalgroup is not limited. Examples of the reactive functional group includealkenyl, hydroxyl, amino, crosslinkable silyl, and polymerizablecarbon-carbon double bond groups. The reactive functional group can beconverted into other appropriate functional group through one or severalsteps. For example, in the present invention, a vinyl polymer having analkenyl group is synthesized by converting a reactive functional groupsuch as hydroxyl group.

Vinyl Polymer Having an Alkenyl Group

The vinyl polymer having an alkenyl group will now be described indetail. The vinyl polymer having an alkenyl group can be used as acomponent of a reactive composition susceptible to hydrosilylation. Forexample, a vinyl polymer having at least one alkenyl group in themolecule is crosslinked by hydrosilylation using a compound having ahydrosilyl group as a curing agent to produce a cured material. A vinylpolymer having at least one alkenyl group in the molecule is subjectedto hydrosilylation with a hydrosilane compound having a crosslinkablefunctional group to produce a vinyl polymer having the crosslinkablefunctional group.

The vinyl polymer having an alkenyl group is prepared by atom transferradical polymerization.

Although the alkenyl group in the present invention is not limited, thealkenyl group is preferably represented by general formula (6):H₂C═C(R¹³)—  (6)(wherein R¹³ represents a hydrogen atom or an organic group of 1 to 20carbon atoms).

In general formula (6), R¹³ represents a hydrogen atom or an organicgroup of 1 to 20 carbon atoms. Although the organic group of 1 to 20carbon atoms is not limited, examples of the organic group of 1 to 20carbon atoms preferably include an alkyl group of 1 to 20 carbon atoms,an aryl group of 6 to 20 carbon atoms, and an aralkyl group of 7 to 20carbon atoms. Examples of the organic group include

-   —(CH₂)_(n)—CH₃, —CH(CH₃)—(CH₂)_(n)—CH₃, —CH(CH₂CH₃)—(CH₂)_(n)—CH₃,-   —CH(CH₂CH₃)₂, —C(CH₃)₂—(CH₂)_(n)—CH₃, —C(CH₃)(CH₂CH₃)—(CH₂)_(n)—CH₃,-   —C₆H₅, —C₆H₅(CH₃), —C₆H₅(CH₃)₂, —(CH₂)_(n)—C₆H₅,    —(CH₂)_(n)—C₆H₅(CH₃), and —(CH₂)_(n)—C₆H₅(CH₃)₂    (wherein n represents an integer of 0 or more, but the total number    of carbons in each organic group is 20 or less).

Among the examples, R¹³ is more preferably a hydrogen atom or a methylgroup.

The alkenyl group is not limited. However, it is not preferable that thealkenyl group in the vinyl polymer is activated by a carbonyl group, analkenyl group, or an aromatic ring, all of which are conjugated with thecarbon-carbon double bond in the alkenyl group in the vinyl polymer.

Although the bond between the alkenyl group and the main chain of thepolymer is not limited, the alkenyl group and the main chain of thepolymer is preferably bonded through, for example, a carbon-carbon bond,an ester bond, an ester bond, a carbonate bond, an amide bond, or aurethane bond.

The vinyl polymer may include the alkenyl groups at any position of themolecule. However, if the cured material of the reactive compositionsusceptible to hydrosilylation according to the present inventionespecially requires an elastic property, at least one of the alkenylgroups is preferably located at one end of the molecular chain becausethis molecular chain structure can increase the molecular weight betweencrosslinks that greatly effects on the rubber elasticity. Morepreferably, the vinyl polymer includes all the alkenyl groups at theends of the molecular chain. That is, all the alkenyl groups are, morepreferably, located at the ends of the molecule.

Although the number of the alkenyl group is not limited, the number ofthe alkenyl group is generally at least 1, preferably, at least 1.2, andmore preferably, at least 1.5 on average in order to produce a highlycrosslinked cured material.

Methods for producing the vinyl polymer having an alkenyl group will nowbe described in detail, which do not intend to limit the scope of thepresent invention.

(A-a) A method for synthesizing a vinyl polymer by atom transfer radicalpolymerization including the step of reacting, for example, a compoundrepresented by general formula (9) as a second monomer, the compoundhaving both a polymerizable alkenyl group and an alkenyl group havinglow polymerizability per molecule:H₂C═C(R¹⁴)—R¹⁵—R¹⁶—C(R¹⁷)═CH₂  (9)(wherein R¹⁴ represents a hydrogen atom or a methyl group; R¹⁵represents —C(O)O— or an o-, m-, p-phenylene group; R¹⁶ represents adirect bond, or a divalent organic group of 1 to 20 carbon atoms, thedivalent organic group may include at least one ether bond; and R¹⁷represents a hydrogen atom or an organic group of 1 to 20 carbon atoms).

In general formula (9), R¹⁷ represents a hydrogen atom or an organicgroup of 1 to 20 carbon atoms. Although the organic group of 1 to 20carbon atoms is not limited, examples of the organic group of 1 to 20carbon atoms preferably include an alkyl group of 1 to 20 carbon atoms,an aryl group of 6 to 20 carbon atoms, and an aralkyl group of 7 to 20carbon atoms. Examples of the organic group include

-   —(CH₂)_(n)—CH₃, —CH(CH₃)—(CH₂)_(n)—CH₃, —CH(CH₂CH₃)—(CH₂)_(CH) ₃,-   —CH(CH₂CH₃)₂, —C(CH₃)₂—(CH₂)_(n)—CH₃, —C(CH₃)(CH₂CH₃)—(CH₂)_(n)—CH₃,-   —C₆H₅, —C₆H₅(CH₃), —C₆H₅(CH₃)₂, —(CH₂)_(n)—C₆H₅,    —(CH₂)_(n)—C₆H₅(CH₃), and —(CH₂)_(n)—C₆H₅(CH₃)₂    (wherein n represents an integer of 0 or more, but the total number    of carbons in each organic group is 20 or less).

Among the examples, R¹⁷ is more preferably a hydrogen atom or a methylgroup.

The compound having both a polymerizable alkenyl group and an alkenylgroup having low polymerizability per molecule may be reacted at anytime during the polymerization. If a cured material produced by curing avinyl polymer requires an elastic property, the compound is preferablyreacted as the second monomer at the end of the polymerization or afterthe reaction of the predetermined monomer.

(A-b) A method for synthesizing a vinyl polymer by atom transfer radicalpolymerization including the step of reacting a compound having at leasttwo carbon-carbon double bonds having low polymerizability, for example,1,5-hexadiene, 1,7-octadiene and 1,9-decadiene, during or after thepolymerization.

(A-c) A method including the step of replacing a halogen atom with analkenyl group by reacting a vinyl polymer produced by atom transferradical polymerization and having at least one highly reactivecarbon-halogen terminal bond with an organometallic compound having analkenyl group such as an organotin, e.g. allyltributyltin orallyltrioctyltin.

(A-d) A method including the step of replacing a halogen atom with analkenyl group by reacting a vinyl polymer produced by atom transferradical polymerization and having at least one highly reactivecarbon-halogen bond at ends of the polymer with a stabilized carbanionhaving an alkenyl group, represented by general formula (10):M⁺C⁻(R¹⁸)(R¹⁹)—R²⁰—C(R¹⁷)═CH₂  (10)(wherein R¹⁷ is as defined above; both R¹⁸ and R¹⁹ represent electronattractive groups that stabilize the carbanion C⁻, or one of R¹⁸ and R¹⁹represents the electron attractive group and the other represents ahydrogen atom, an alkyl group of 1 to 20 carbon atoms or a phenyl group;R²⁰ represents a direct bond or a divalent organic group of 1 to 20carbon atoms, the divalent organic group may include at least one etherbond; and M+represents an alkali metal ion or a quaternary ammoniumion).

Examples of the electron attractive groups R¹⁸ and R¹⁹ include —CO₂R(ester group), —C(O)R (keto group), —CON(R₂) (amido group), —COSR(thioester group), —CN (nitrile group), and —NO₂ (nitro group). Inparticular, —CO₂R (ester group), —C(O)R (keto group) and —CN (nitrilegroup) are preferable. The substituent R represents an alkyl group of 1to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, or an aralkylgroup of 7 to 20 carbon atoms. The substituent R is preferably an alkylgroup of 1 to 10 carbon atoms or a phenyl group.

(A-e) A method including the steps of preparing an enolate anion byreacting a vinyl polymer having at least one highly reactivecarbon-halogen terminal bond produced by atom transfer radicalpolymerization with a metal such as zinc or an organometallic compound;and reacting the resultant product with an electrophilic compound havingan alkenyl group, for example, a compound including an alkenyl grouphaving a leaving group such as a halogen atom or acetyl group, acarbonyl compound having an alkenyl group, an isocyanate compound havingan alkenyl group, or an acid halide having an alkenyl group.

(A-f) A method including the step of replacing a halogen atom with analkenyl group by reacting a vinyl polymer produced by atom transferradical polymerization and having at least one highly reactivecarbon-halogen terminal bond with an oxyanion having an alkenyl group ora carboxylate anion having an alkenyl group, for example, represented bygeneral formula (11) or (12):H₂C═C(R¹⁷)—R²¹—O⁻M⁺  (11)(wherein R¹⁷ and M⁺ are as defined above, R²¹ represents a divalentorganic group of 1 to 20 carbon atoms, the divalent organic group mayinclude at least one ether bond); orH₂C═C(R¹⁷)—R²²—C(O)O⁻M⁺  (12)(wherein R¹⁷ and M⁺ are as defined above, R²² represents a direct bondor a divalent organic group of 1 to 20 carbon atoms, the divalentorganic group may include at least one ether bond).

In terms of ready control of the reaction, among Methods (A-a) to (A-f),Methods (A-b) and (A-f) are preferable. Methods (A-b) and (A-f) will nowbe described in detail.

Method for Adding Diene Compound [Method (A-b)]

Method (A-b) includes the step of reacting a vinyl polymer produced byatom transfer radical polymerization of a vinyl monomer with a compoundhaving at least two alkenyl groups having low polymerizability(hereinafter referred to as diene compound).

These at least two alkenyl groups in the diene compound may be the sameor different. The alkenyl groups may be either terminal alkenyl groups[CH₂═C(R)—R′; wherein R represents a hydrogen atom or an organic groupof 1 to 20 carbon atoms, R′ represents an organic group of 1 to 20carbon atoms, and R and R′ may bond to each other at their ends to forma cyclic structure.] or internal alkenyl groups [R′—C(R)═C(R)—R′;wherein R represents a hydrogen atom or an organic group of 1 to 20carbon atoms, R′ represents an organic group of 1 to 20 carbon atoms,and two Rs (or two R′s) may be the same or different, any twosubstituents of the two Rs and two R′s may bond to each other at theirends to form a cyclic structure.]. The terminal alkenyl groups are morepreferable. R represents a hydrogen atom or an organic group of 1 to 20carbon atoms. The organic group of 1 to 20 carbon atoms preferablyincludes an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to20 carbon atoms, and an aralkyl group of 7 to 20 carbon atoms. Morepreferably, R is a hydrogen atom or a methyl group.

Among the alkenyl groups of the diene compound, at least two alkenylgroups may be conjugated.

Examples of the diene compound include isoprene, piperylene, butadiene,myrcene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, and4-vinyl-1-cyclohexene. In particular, 1,5-hexadiene, 1,7-octadiene, and1,9-decadiene are preferable.

A vinyl monomer is subjected to living radical polymerization, and theresultant polymer is isolated from the polymerization system.Subsequently, the isolated polymer and the diene compound may besubjected to radical reaction to produce a desired vinyl polymer havingterminal alkenyl groups. Alternatively, the diene compound may be addedto the polymerization reaction system during polymerization or after thepolymerization and, preferably, at the end of the polymerizationreaction or after the reaction of the predetermined vinyl monomer, dueto simplicity of the reaction.

The additive content of the diene compound must be controlled dependingon the radical reactivity of the alkenyl groups in the diene compound.When the two alkenyl groups are significantly different in reactivity,the content of the diene compound may be the equivalent or a slightexcess of the propagating ends in the polymer. On the other hand, whenthe two alkenyl groups have the same or similar reactivity, both the twoalkenyl groups are reacted and the polymer ends are subjected tocoupling. Therefore, the content of the diene compound is preferablylarger than the content of the propagating ends in the polymer. Theadditive content of the diene compound is preferably at least 1.5 times,more preferably, at least 3 times, and most preferably, at least 5 timesof the propagating ends in the polymer.

Nucleophilic Substitution Method [Method (A-f)]

Method (A-f) includes the step of replacing a halogen atom with analkenyl group by reacting a vinyl polymer produced by atom transferradical polymerization and having at least one highly reactivecarbon-halogen terminal bond with an oxyanion having an alkenyl group ora carboxylate anion having an alkenyl group.

The oxyanion having an alkenyl group or the carboxylate anion having analkenyl group is not limited. Examples of the oxyanions or carboxylateanions are represented by general formula (11) or (12):H₂C═C(R¹⁷)—R²¹—O⁻M⁺  (11)(wherein R¹⁷ and M⁺ are as defined above, R²¹ represents a divalentorganic group of 1 to 20 carbon atoms, the divalent organic group mayinclude at least one ether bond); orH₂C═C(R¹⁷)—R²²—C(O)O⁻M⁺  (12)(wherein R¹⁷ and M⁺ are as defined above, R²² represents a direct bondor a divalent organic group of 1 to 20 carbon atoms, the divalentorganic group may include at least one ether bond).

Examples of the oxyanion or carboxylate anion include salts of alkenylalcohols such as allyl alcohol; salts of allyloxy alcohols such asethylene glycol monoallylether; salts of phenolic hydroxyl groupscontaining alkenyl groups such as allyl phenol and allyloxy phenol;carboxylates containing alkenyl groups such as 10-undecylenic acid,4-pentenoic acid, and vinyl acetate.

M⁺ is a counter cation. Examples of the counter cation M⁺ include alkalimetal ions such as lithium ion, sodium ion, and potassium ion; andquaternary ammonium ions. Examples of the quaternary ammonium ionsinclude tetramethylammonium ion, tetraethylammonium ion,tetrabenzylammonium ion, trimethyldodecylammonium ion,tetrabutylammonium ion, and dimethylpiperidinium ion. Preferably, thecounter cation M⁺ is sodium ion, and potassium ion.

The content of the oxyanion or carboxylate anion may be excess to thehalogen atoms in the vinyl polymer, and is preferably, 1 to 5equivalents, more preferably, 1 to 2 equivalents, and most preferably,1.0 to 1.2 equivalents of the halogen atoms in the vinyl polymer.

Although solvents used for this reaction are not limited, solventshaving relatively high polarity are preferable. Examples of the solventinclude ethers such as diethyl ether, tetrahydrofuran, diphenyl ether,anisole, and dimethoxybenzene; halogenated hydrocarbons, such asmethylene chloride and chloroform; ketones such as acetone, methyl ethylketone, and methyl isobutyl ketone; alcohols such as methanol, ethanol,propanol, isopropyl alcohol, n-butyl alcohol, and tert-butyl alcohol;nitrites such as acetonitrile, propionitrile, and benzonitrile; esterssuch as ethyl acetate and butyl acetate; carbonates such as ethylenecarbonate and propylene carbonate; and amides such as dimethylformamide,dimethylacetamide, and hexamethylphosphoric triamide; and sulfoxidessuch as dimethylsulfoxide. These solvents may be used alone or incombination. In particular, polar solvents, for example, acetone,dimethylsulfoxide, dimethylformamide, dimethylacetamide,hexamethylphosphoric triamide, and acetonitrile are preferable. Althoughthe reaction temperature is not limited, the reaction temperature isgenerally 0° C. to 150° C. and preferably room temperature to 100° C.

Furthermore, reaction accelerators such as amines, ammonium salts, andcrown ethers may be added to the reaction system.

Instead of the oxyanion or the carboxylate anion, alcohols or carboxylicacids, which are the precursors, may react with bases in the reactionsystem to prepare the oxyanion or the carboxylate anion.

When the vinyl polymer includes ester groups in the side chains or themain chain, a less nucleophilic carboxylate anion is preferably used. Ahighly nucleophilic oxyanion may cause ester interchange.

Methods for Converting a Hydroxyl Group into an Alkenyl Group

A vinyl polymer having at least one alkenyl group can be produced from avinyl polymer having at least one hydroxyl group. Examples of the methodare described below, but are not limited to the following methods.

(A-g) A method including the steps of reacting a hydroxyl group in avinyl polymer having at least one hydroxyl group with a base such assodium methoxide, and reacting the product with an alkenyl halide suchas allyl chloride.

(A-h) A method including the step of reacting a hydroxyl group in avinyl polymer having at least one hydroxyl group with an alkenylisocyanate such as allyl isocyanate.

(A-i) A method including the step of reacting a hydroxyl group in avinyl polymer having at least one hydroxyl group with an acid halidecontaining an alkenyl group such as (meth)acryloyl chloride and10-undecenoyl chloride in the presence of a base such as pyridine.

(A-j) A method including the step of reacting a hydroxyl group in avinyl polymer having at least one hydroxyl group with a carboxylic acidcontaining an alkenyl group such as acrylic acid, pentenoic acid, and10-undecenoic acid in the presence of an acid catalyst.

(A-k) A method including the steps of reacting a vinyl polymer having ahydroxyl group with a diisocyanate compound; and reacting the residualisocyanate group with a compound having both an alkenyl group and ahydroxyl group. Although the compound having both an alkenyl group and ahydroxyl group is not limited, examples of the compound include alkenylalcohols such as 10-undecenol, 5-hexenol, and allyl alcohol.

Any known diisocyanate compound may be used. Examples of thediisocyanate compound include isocyanate compounds such as toluylenediisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethyldiisocyanate, xylylene diisocyanate, meta-xylylene diisocyanate,1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate,hydrogenated toluylene diisocyanate, hydrogenated xylylene diisocyanate,and isophorone diisocyanate. These compounds may be used alone or incombination. Blocked isocyanates may be also used.

Diisocyanate compounds not having an aromatic ring, for example,hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanateare preferably used in order to achieve superior weather resistance.

Methods for Synthesizing a Vinyl Polymer Having a Hydroxyl Group

Examples of the method for producing a vinyl polymer having at least onehydroxyl group are described below, but are not limited to the followingmethods.

(B-a) A method for synthesizing a vinyl polymer by atom transfer radicalpolymerization including the step of a reaction of, for example, acompound having both a polymerizable alkenyl group and a hydroxyl groupper molecule as a second monomer, the compound represented by generalformula (15):H₂C═C(R¹⁴)—R¹⁵—R¹⁶—OH  (15)(wherein R¹⁴, R¹⁵, and R¹⁶ are as defined above).

The compound having both a polymerizable alkenyl group and a hydroxylgroup per molecule may be reacted at any time during the polymerization.If the polymer requires an elastic property, especially in livingradical polymerization, the compound is preferably reacted as the secondmonomer at the end of the polymerization or after the reaction of thepredetermined monomer.

(B-b) A method for synthesizing a vinyl polymer by atom transfer radicalpolymerization including the step of a reaction of an alkenyl alcoholsuch as 10-undecenol, 5-hexenol, and allyl alcohol at the end of thepolymerization or after the reaction of the predetermined monomer.

(B-c) A method including the step of replacing a halogen atom with aterminal hydroxyl group by hydrolyzing or reacting a vinyl polymerproduced by atom transfer radical polymerization and having at least onehighly reactive carbon-halogen terminal bond with a compound containinga hydroxyl group.

(B-d) A method including the step of replacing a halogen atom with ahydroxyl group by reacting a vinyl polymer produced by atom transferradical polymerization and having at least one highly reactivecarbon-halogen terminal bond with a stabilized carbanion having ahydroxyl group represented by general formula (16):M⁺C⁻(R¹⁸)(R¹⁹)—R²⁰—OH  (16)(wherein R¹⁸, R¹⁹ and R²⁰ are as defined above).

Examples of the electron attractive groups R¹⁸ and R¹⁹ include —CO₂R(ester group), —C(O)R (keto group), —CON(R₂) (amido group), —COSR(thioester group), —CN (nitrile group), and —NO₂ (nitro group). Inparticular, —CO₂R (ester group), —C(O)R (keto group) and —CN (nitrilegroup) are preferable. The substituent R represents an alkyl group of 1to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, or an aralkylgroup of 7 to 20 carbon atoms. The substituent R is preferably an alkylgroup of 1 to 10 carbon atoms or a phenyl group.

(B-e) A method including the steps of preparing an enolate anion byreacting a vinyl polymer produced by atom transfer radicalpolymerization and having at least one highly reactive carbon-halogenterminal bond with a metal such as zinc or an organometallic compound;and reacting the resultant product with an aldehyde or a ketone.

(B-f) A method including the step of replacing a halogen atom with ahydroxyl group by reacting a vinyl polymer produced by atom transferradical polymerization and having at least one highly reactivecarbon-halogen terminal bond with an oxyanion having a hydroxyl group ora carboxylate anion having a hydroxyl group, for example, represented bygeneral formula (17) or (18):HO—R²¹—O⁻M⁺  (17)(wherein R²¹ and M⁺ are as defined above); orHO—R²²—C(O)O⁻M⁺  (18)(wherein R²² and M⁺ are as defined above).

All examples of M⁺, the reaction conditions, and solvent described inMethod (A-f) can be preferably used.

(B-g) A method for synthesizing a vinyl polymer by atom transfer radicalpolymerization including the step of a reaction of a compound havingboth an alkenyl group having low polymerizability and a hydroxyl groupper molecule as a second monomer at the end of the polymerization orafter the reaction of the predetermined monomer. Although the compoundis not limited, examples of the compound include compounds representedby general formula (19):H₂C═C(R¹⁴)—R²¹—OH  (19)(wherein R¹⁴ and R²¹ are as defined above).

The compounds represented by general formula (19) are not limited. Interms of availability, alkenyl alcohols such as 10-undecenol, 5-hexenol,and allyl alcohol are preferable.

In terms of ready control of the reaction, among Methods (B-a) to (B-g),Methods (B-b) and (B-f) are preferable.

Treatment with an adsorbent will now be described.

According to the method of the present invention, a vinyl monomer ispolymerized by atom transfer radical polymerization, and then theresultant vinyl polymer is brought into contact with the adsorbent inthe presence of an oxidizing agent.

The treatment with the adsorbent may be performed either on the vinylpolymer (crude product) that is the final product, or on an intermediateproduct to produce the vinyl polymer. In other words, the treatment withthe adsorbent may be performed on any vinyl polymers, such as vinylpolymers having alkenyl groups, vinyl polymers having highly reactivecarbon-halogen (in particular, bromine) bonds, vinyl polymers havinghydroxyl groups, and other vinyl polymers.

The oxidizing agent used in the method of the present invention includesoxygen molecules and/or a substance that forms oxygen molecules by areaction. Examples of the oxidizing agent are described below, but donot intend to limit the scope of the present invention.

(C-a) Heavy Metal Compounds

Examples of the heavy metal compound include manganese dioxide;permanganates such as sodium permanganate, potassium permanganate;manganese salts such as manganese acetate, manganese sulfate, andmanganese pyrophosphate; chromium trioxide; dichromates such as sodiumdichromate, potassium dichromate, and ammonium dichromate; chromylchloride; tert-butyl chromate; chromyl acetate; lead tetraacetate; leadoxide; mercury acetate; mercury oxide; osmium tetroxide; rutheniumtetroxide; and selenium dioxide.

(C-b) Halogens

Examples of the halogen include halogens such as chlorine, bromine,iodine; interhalogen compounds such as chlorine fluoride, chlorinetrifluoride, bromine trifluoride, bromine pentafluoride, brominechloride, and iodine chloride.

(C-c) Nitroxide Compounds

Examples of the nitroxide compound include nitric acid; nitrates such assodium nitrate, potassium nitrate, and ammonium nitrate; nitrites suchas sodium nitrite and potassium nitrite; and nitrogen oxides such asdinitrogen oxide, dinitrogen trioxide, and nitrogen dioxide.

(C-d) Compounds Including Halogen and Oxygen Atoms

Examples of the compounds including halogen and oxygen atoms includechlorine dioxide; perhalogenic acids such as perchloric acid andperiodic acid; chlorates such as sodium chlorate, potassium chlorate,and ammonium chlorate; perchlorates such as sodium perchlorate,potassium perchlorate, and ammonium perchlorate; chlorites such assodium chlorite and potassium chlorite; hypochlorites such as sodiumhypochlorite and calcium hypochlorite; bromates such as sodium bromateand potassium bromate; iodates such. as sodium iodate and potassiumiodate; and periodates such as sodium periodate and potassium periodate.

(C-e) Metal Peroxides

Examples of the metal peroxide include alkali metal peroxides such assodium peroxide and potassium peroxide; and alkaline earth metalperoxides such as magnesium peroxide, calcium peroxide, and bariumperoxide.

(C-f) Organic Peroxides

Examples of the organic peroxide include alkyl hydroperoxides such astert-butyl hydroperoxide and cumyl hydroperoxide; diacyl peroxides suchas dibenzoyl peroxide, di-p-nitrobenzoyl peroxide, anddi-p-chlorobenzoyl peroxide; organic peracids such as peracetic acid,trifluoroperacetic acid, perbenzoic acid, meta-chloroperbenzoic acid,monoperphthalic acid, and performic acid; peracid esters such astert-butyl peracetate and tert-butyl perbenzoate; and dialkyl peroxidessuch as ditert-butyl peroxide.

(C-g) Hydrogen Peroxide and its Derivatives

Examples of the hydrogen peroxide and its derivative include hydrogenperoxide; sodium percarbonate; perborates such as sodium perborate andpotassium perborate; and urea peroxide. When these compounds aredissolved in water or are thermally degraded, these compounds generatehydrogen peroxide.

(C-h) Oxygen (Oxygen Molecule) and Ozone

Examples of the oxidizing agent further include persulfates such assodium persulfate, potassium persulfate, and ammonium persulfate;potassium nitrosodisulfonate; and trichloroisocyanuric acid.

These oxidizing agents may be used alone or in combination. In terms ofease of handling and removing residue after the treatment of thepolymer, the oxidizing agents preferably include the oxidizing agentsdescribed in Items (C-c) to (C-h), more preferably, hydrogen peroxide,its derivatives, oxygen, or ozone, and more preferably oxygen.

When oxygen is used as the oxidizing agent, the oxygen may be pureoxygen or an oxygen-containing gaseous mixture. Although the gas otherthan oxygen in the oxygen-containing gaseous mixture is not limited, thegas preferably includes inert gases such as nitrogen, helium, and argon.In particular, a mixed gas containing oxygen and nitrogen is preferable.When the oxygen-containing system includes an organic solvent, theoxygen concentration is preferably controlled to be less than thecombustion threshold in order to avoid an explosion hazard.

The content of the oxidizing agent is not limited. When oxygen or ozoneis used as the oxidizing agent, the content of the oxidizing agent ispreferably as follows: The oxidizing agent contains oxygen atoms of,preferably, 0.1 to 5,000 molar ratio, more preferably 0.1 to 10 molarratio, and most preferably, 0.1 to 5 molar ratio to the total transitionmetal in the reaction system. When a substance other than oxygen orozone is used as the oxidizing agent, the content of the oxidizing agentis preferably as follows: The oxidizing agent contains oxygen atoms of,preferably, 0.1 to 100 molar ratio, more preferably 0.1 to 100 molarratio, and most preferably, 0.1 to 10 molar ratio to the totaltransition metal in the reaction system.

Examples of the adsorbent used in the method of the present inventionare described in the following Items (D-a) to (D-c). The adsorbent ofthe present invention is not limited to the following examples.

(D-a) Activated Carbon

Most part of activated carbon is composed of carbonaceous materials, andactivated carbon has high adsorptivity. For example, the activatedcarbon is produced as follows: Wood, brown coal, or peat is treated withan activating agent such as zinc chloride and phosphoric acid and issubjected to dry distillation. Alternatively, charcoal is activated bywater vapor. The activated carbon is generally powdered or granular.Both powdered and granular activated carbon may be used. Chemicallyactivated carbon is acidic whereas activated carbon by water vaportreatment is basic due to the producing process.

(D-b) Synthetic Resin Adsorbents

Example of synthetic resin adsorbents includes ion exchange resins.General acidic ion exchange resins and basic ion exchange resins may beused as the ion exchange resins. Chelate ion exchange resins may also beused. Examples of the functional groups of the acidic ion exchangeresins include a carboxylic acid group and sulfonic acid group; examplesof the functional groups of the basic ion exchange resins include anamino group, and examples of the functional groups of the chelate ionexchange resins include an iminodiacetic acid group and polyamine group.

(D-c) Inorganic Adsorbents

Inorganic adsorbents are each solid acid, solid base, or neutral. Theinorganic adsorbents have high adsorption capacity due to the porousstructure of the particles. Furthermore, the inorganic adsorbents arecharacterized in that they can be used at a wide range of temperature.The inorganic adsorbent is not limited. Typical examples of theinorganic adsorbent are mainly composed of at least one of, for example,aluminum, magnesium, and silicon. Examples of the inorganic adsorbentinclude silicon dioxide; magnesium oxide; silica gel; silica-alumina,aluminum silicate; magnesium silicate; activated alumina; clayadsorbents such as acid clay and activated clay; zeolite adsorbents thatare generically named as hydrous aluminosilicate minerals such asaluminum sodium silicate; dawsonites; and hydrotalcites.

Examples silicon dioxide may be crystalline, amorphous, noncrystalline,glassy, synthetic, or natural. Any powdery silicon dioxide may be used.Examples of silicon dioxide include silicic acid produced from clayminerals prepared by acid treatment of activated clay; and syntheticsilicic acid such as Carplex BS304, Carplex BS304F, Carplex #67, andCarplex #80 (Shionogi & Co., Ltd.). Silicon dioxide is not limited tothe above examples.

In aluminum silicate, silicon in silicic acid is partially replaced withaluminum. Examples of aluminum silicate include pumice, fly ash, kaolin,bentonite, activated clay, and diatomaceous earth. In particular,synthetic aluminum silicate has a large specific surface area and highadsorption capacity. Although examples of the synthetic aluminumsilicate include Kyowaad 700 series (Kyowa Chemical Industry Co., Ltd.),the synthetic aluminum silicate is not limited to the above.

Both natural zeolite and synthetic zeolite may be used.

In hydrotalcite compounds, hydroxyl groups of aqueous hydroxides of adivalent metal (for example, Mg²⁺, Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, orZn²⁺) and a trivalent metal (for example, Al³⁺, Fe³⁺, Cr³⁺, Co³⁺, orIn³⁺) or hydroxyl groups of the hydroxides are partially replaced withan anion such as halide ions, NO₃ ⁻, CO₃ ²⁻, SO₄ ²⁻, Fe(CN)₆ ³⁻, CH₃CO₂⁻, oxalate ion, or salicylate ion. A hydrotalcite is preferable in whichthe divalent metal is Mg²⁺, the trivalent metal is Al³⁺, and thehydroxyl groups is replaced with CO₃ ²⁻. Although examples of thesynthesized hydrotalcite include Kyowaad 500 series and Kyowaad 1000series (Kyowa Chemical Industry Co., Ltd.), the hydrotalcite is notlimited to the above. Furthermore, adsorbents produced by firing theabove hydrotalcites are also preferably used. In particular, an MgO-AlO₃solid solution produced by firing a hydrotalcite is preferable in whichthe divalent metal is Mg²⁺ and the trivalent metal is Al³⁺. Althoughexamples of the fired hydrotalcite include Kyowaad 2000 (Kyowa ChemicalIndustry Co., Ltd.), the hydrotalcite is not limited to the above.According to the present invention, the fired products of thehydrotalcites are also referred to as hydrotalcites.

The adsorbents are preferably inorganic adsorbents or activated carbon,more preferably, magnesium oxide, activated clay, aluminum silicate,activated alumina, or hydrotalcites, and most preferably, aluminumsilicate or hydrotalcites. In particular, both aluminum silicate andhydrotalcites are preferably used together.

The adsorbents may be used alone or in combination.

The content of the adsorbent may be generally 0.1 to 500 parts by weightto 100 parts by weight of the vinyl polymer. In view of economicalefficiency and handling, the content of the adsorbent is preferably 0.5to 10 parts by weight, more preferably, 0.5 to 5 parts by weight to 100parts by weight of the vinyl polymer.

According to the purification process in the method of the presentinvention, the vinyl polymer may be brought into contact with theadsorbent in the presence of the oxidizing agent. Alternatively, theoxidizing agent may be brought into contact with the vinyl polymer, andthen the adsorbent may be brought into contact with the vinyl polymer.

A method including the step of bringing the vinyl polymer into contactwith the adsorbent in the presence of the oxidizing agent will now bedescribed.

When oxygen or ozone is used as the oxidizing agent, the adsorbent maybe brought into contact with the vinyl polymer in a system containingoxygen or ozone. This process may be performed in the presence of asolvent or in a solvent-free system.

Various methods are available for the gas-liquid contact between oxygenor ozone and the vinyl polymer or the solution of the vinyl polymer, andthe methods are not limited. Specifically, examples of methods includebatch processes by stirring and by gas bubbling through an orifice, anda bubble column process of bubbling gas through the polymer solution ina container. In addition to the mixing and dispersion by stirring, ifnecessary, other operations, for example, shaking of the container andultrasonic waves may be employed in order to improve the dispersionefficiency. When the mixing is performed by stirring, the vapor-phase inthe container is preliminarily filled with gas. In some cases, a singlefilling operation cannot supply a required amount of gas. In this case,appropriate replacement or supplement of the gas in the vapor-phase canbe performed to continue the oxidation treatment.

When the oxidizing agent other than oxygen and ozone is used, themixture of the oxidizing agent and the vinyl polymer is brought intocontact with the adsorbent. This process may be performed in thepresence of a solvent or in a solvent-free system.

The solvents used in the purification process in the method of thepresent invention are not limited. Examples of the solvent includealiphatic hydrocarbons such as n-hexane, n-heptane, n-octane,cyclohexane, methylcyclohexane, and ethylcyclohexane; aromatichydrocarbons such as toluene and xylenes; fatty acid esters such asbutyl acetate; and ethers such as diethyl ether. Preferably, n-hexane,cyclohexane, methylcyclohexane, ethylcyclohexane, toluene, xylenes,butyl acetate, and diethyl ether are used.

In particular, the relative dielectric constant at 25° C. of the solventis preferably 5 or less. The reason is as follows: Although the vinylpolymer is dissolved in a solvent having low polarity, the remainingtransition metal complex can become insolubilized and coalesced. Asolvent having a low relative dielectric constant is a poor solvent ofthe transition metal complex. Accordingly, the addition of a solventhaving a low relative dielectric constant facilitates insolubilizationof the transition metal complex, and the insolubilized transition metalcomplexes collide with each other to coalesce. The insolubilized andcoalesced transition metal complex and transition metal are readilyremoved by the adsorbent.

According to the present invention, insolubilization is defined asfollows: The solid content of the transition metal complex that cannotbe dissolved and is precipitated is 0.1 weight percent or more relativeto the total weight of the transition metal complex in the solution.

According to the present invention, coalescence is defined as follows:In a dynamic light scattering measurement, the relaxation time of theintensity correlation function increases in the range of 1 millisecondto 1,000 milliseconds. In the dynamic light scattering measurement, atime-series light scattering measurement is continuously performedwithin the measuring time range from 1 minute to 72 hours. Therelaxation times of the intensity correlation function at individualelapsed times are compared.

(Dynamic Light Scattering Measurement)

A dynamic light scattering instrument DLS 7000 (Otsuka Electronics Co.,Ltd.) and analysis software ALV 5000 (ALV of Germany) are used. Anexample of the laser used in the measurement includes a visible lightlaser such as a helium-neon laser and argon laser. A sufficient laseroutput is 75 mW or more. A laser output less than 35 mW impairs theaccuracy of the measurement. With regard to the measurement conditions,the scattering angle is from 30° to 150°, preferably, from 60° to 120°,and the measuring temperature is from 5° C. to 100° C., preferably, from20° C. to 40° C. In the present invention, in order to confirm thecoalescence of the transition metal complex, the relaxation times weremeasured under the following conditions: The laser output was 70 mW, thescattering angle was 90°, and the measuring temperature was 25° C.

The solvents that have a relative dielectric constant of 5 or less at25° C. are not limited. Examples of the solvent include aliphatichydrocarbons such as n-hexane, n-heptane, n-octane, cyclohexane,methylcyclohexane, and ethylcyclohexane; and aromatic hydrocarbons suchas toluene and xylenes. These solvents may be used alone or incombination as long as the polymer can be dissolved.

The content of the solvent is generally 10 to 1,000 parts by weight,preferably, 50 to 500 parts by weight relative to 100 parts by weight ofthe vinyl polymer. A content of the solvent less than 10 parts by weightdecreases the effect of insolubilization and coalescence. On the otherhand, a content of the solvent exceeding 1,000 parts by weight no longerimprove the insolubilization effects. Furthermore, in view of therecovering cost of the solvents, this is actually a wastefulmanufacturing process.

The apparatus used for dissolving the polymer in the solvent is notlimited. For example, a general-purpose stirring tank may be used in abatch process, whereas a line mixer may be used in a continuous process.

Various methods are available for the solid-liquid contact between theadsorbent and the vinyl polymer or the solution of the vinyl polymer,and the methods are not limited. Specifically, examples of the methodinclude a batch process including stirring and solid-liquid separationperformed by an batch operation, a fixed-bed process allowing thepolymer solution to flow through the adsorbent filled in a container, amoving-bed process allowing the polymer solution to flow through amoving-bed having the adsorbent, and a fluidized-bed process forperforming the adsorption by fluidizing the adsorbent with the polymersolution. In addition to the mixing and dispersion by stirring, ifnecessary, other operations, for example, shaking of the container andultrasonic waves may be employed in order to improve the dispersionefficiency.

In the treatment with the adsorbent, adding water to the vinyl polymeror the solution of the vinyl polymer can decrease the content of thetransition metal complex in the solution of the vinyl polymer. Theinsolubilized transition metal complex has a strong affinity with water.Therefore, adding water can concentrate the transition metal complex inthe aqueous phase. Since the specific gravity of the water containingthe transition metal complex is considerably larger than that of thepolymer solution, the transition metal complex is readily separated bycentrifugation or filtration. Furthermore, the transition metal complexcan be separated by simpler methods such as plain sedimentation.

The additive content of water is generally 0.1 to 1,000 molar ratio,preferably 0.1 to 500 molar ratio to the total of the transition metalin the reaction system. Before the solid-liquid separation, water may beadded at any time by any method.

The temperature during the contact is not limited, and is generally 0°C. to 250° C., preferably, 20° C. to 250° C., and more preferably, 80°C. to 250° C. High temperature is preferable because the coalescence ofthe transition metal complex is accelerated and the purification of thevinyl polymer is facilitated. However, an excessively high temperaturemay impair the quality of the vinyl polymer.

Also, the duration of the treatment is not limited, as long as theobject of the present invention can be achieved. The treatment cangenerally be performed for about 30 minutes to about 300 minutes.

The polymer or the polymer solution is brought into contact with theadsorbent, and then the adsorbent is removed by, for example,filtration, centrifugation, or plain sedimentation. If necessary,dilution and water washing may be employed. Thus, a desired polymer orpolymer solution can be recovered.

A method including the steps of bringing the oxidizing agent intocontact with the vinyl polymer, and then bringing the adsorbent intocontact with the vinyl polymer will now be described.

When oxygen or ozone is used as the oxidizing agent, the vinyl polymermay be brought into contact with oxygen or ozone in a system containingoxygen or ozone, and then the adsorbent may be brought into contact withthe vinyl polymer. Both of the processes may be performed in thepresence of a solvent or in a solvent-free system. As described above,both of the processes may be performed in the presence of water.

When an oxidizing agent other than oxygen and ozone is used, theoxidizing agent and the vinyl polymer may be mixed, the oxidizing agentmay be brought into contact with the vinyl polymer (preferably bystirring), and then the adsorbent may be brought into contact with thevinyl polymer. Both of the processes may be performed in the presence ofa solvent or in a solvent-free system. Examples of the solvent includethe same described above. Furthermore, as described above, both of theprocesses may be performed in the presence of water.

Various methods are available for the gas-liquid contact between oxygenor ozone and the vinyl polymer or the solution of the vinyl polymer, andthe methods are not limited. Specifically, examples of methods includebatch processes by stirring and by gas bubbling through an orifice, anda bubble column process of bubbling gas through the polymer solution ina container. In addition to the mixing and dispersion by stirring, ifnecessary, other operations, for example, shaking of the container andultrasonic waves may be employed in order to improve the dispersionefficiency. When the mixing is performed by stirring, the vapor-phase inthe container is preliminarily filled with gas. In some cases, a singlefilling operation cannot supply a required amount of gas. In this case,appropriate replacement or supplement of the gas in the vapor-phase canbe performed to continue the oxidation treatment.

When the oxidizing agent is brought into contact with the vinyl polymer,the temperature is generally 0° C. to 250° C., preferably, 20° C. to250° C., and more preferably, 80° C. to 250° C.

Also, the duration of the treatment is not limited, as long as theobject of the present invention can be achieved. The treatment can begenerally performed for about 30 minutes to about 300 minutes.

Various methods are available for the solid-liquid contact between theadsorbent and the vinyl polymer or the solution of the vinyl polymer,and the methods are not limited. Specifically, examples of the methodinclude a batch process including stirring and solid-liquid separationperformed by an batch operation, a fixed-bed process allowing thepolymer solution to flow through the adsorbent filled in a container, amoving-bed process allowing the polymer solution to flow through amoving-bed having the adsorbent, and a fluidized-bed process forperforming the adsorption by fluidizing the adsorbent with the polymersolution. In addition to the mixing and dispersion by stirring, ifnecessary, other operations, for example, shaking of the container andthe use of ultrasonic waves may be used in order to improve thedispersion efficiency.

When the adsorbent is brought into contact with the vinyl polymer, thetemperature is not limited. The temperature is generally 0° C. to 250°C., preferably, 20° C. to 250° C., and more preferably, 80° C. to 250°C. High temperature is preferable because the coalescence of thetransition metal complex is accelerated and the purification of thevinyl polymer is facilitated. However, an excessively high temperaturemay impair the quality of the vinyl polymer.

Also, the duration of the contact is not limited, as long as the objectof the present invention can be achieved. The contact process can begenerally performed for about 30 minutes to about 300 minutes.

The polymer or the polymer solution is brought into contact with theadsorbent, and then the adsorbent is removed by, for example,filtration, centrifugation, or plain sedimentation. If necessary,dilution and water washing may be employed. Thus, a desired polymer orpolymer solution can be recovered.

According to a first preferable embodiment of the present invention, avinyl monomer is polymerized by atom transfer radical polymerization inthe presence of a polymerization solvent with a transition metal complexas a polymerization catalyst, subsequently the polymerization solvent isremoved, and the resultant vinyl polymer can be brought into contactwith the adsorbent in the presence of the oxidizing agent.

According to a second preferable embodiment of the present invention, avinyl monomer is polymerized by atom transfer radical polymerizationwith a transition metal complex as a polymerization catalyst,subsequently, if necessary, a polymerization solvent is removed, and theresultant vinyl polymer is brought into contact with the adsorbent inthe presence of the oxidizing agent and a solvent (a first contactprocess). Furthermore, the vinyl polymer can be brought into contactwith the adsorbent in the presence of the oxidizing agent in asolvent-free system (a second contact process). In this case, thetransition metal is roughly removed in the first contact process, andthe purity of the vinyl polymer can be further improved in the secondcontact process. A reaction to convert the functional groups of thevinyl polymer may be performed between the first contact process and thesecond contact process.

Reactive Composition Susceptible to Hydrosilylation

The reactive composition susceptible to hydrosilylation of the presentinvention includes the vinyl polymer produced by the method of thepresent invention.

Examples of the reactive composition susceptible to hydrosilylation ofthe present invention include reactive compositions susceptible tohydrosilylation containing vinyl polymers (A) having alkenyl groups inthe molecule and compounds (B) having hydrosilyl groups.

The vinyl polymers (A) may be the above-mentioned vinyl polymers havingalkenyl groups in the molecule produced by atom transfer radicalpolymerization. The compounds (B) having hydrosilyl groups are notlimited and various compounds can be used. Examples of the compounds (B)having hydrosilyl groups include a compound having at least 1.1hydrosilyl groups per molecule and hydrosilane compounds havingcrosslinkable silyl groups. Examples of the reactive compositionssusceptible to hydrosilylation are described below.

<Reactive Composition Susceptible to Hydrosilylation (1)>

Compounds (B) having at least 1.1 hydrosilyl groups per molecule formcured materials by hydrosilylation. That is, the reactive compositionssusceptible to hydrosilylation are curable compositions (curablecomposition (1)).

The compounds having at least 1.1 hydrosilyl groups per molecule are notlimited. Examples of the compound include polysiloxanes represented bygeneral formula (22) or (23):R²³ ₃SiO—[Si (R²³)₂O]_(a)—[Si(H)(R²⁴)O]_(b)—[Si(R²⁴)(R²⁵)O]_(c)—SiR²³₃  (22)HR²³ ₂SiO—[Si(R²³)₂O]_(a)—[Si(H)(R²⁴)O]_(b)—[Si(R²⁴)(R²⁵)O]_(c)—SiR²³₂H  (23)(wherein each of R²³ and R²⁴ represents an alkyl group of 1 to 6 carbonatoms, or a phenyl group; R²⁵ represents an alkyl group of 1 to 10carbon atoms or an aralkyl group of 1 to 10 carbon atoms; and a, b, andc independently represent an integer that satisfies the followingformulae: 100≧a≧0, 100≧b≧2, and 100≧c≧0), and

-   cyclosiloxanes represented by general formula (24):

(wherein each of R²⁶ and R²⁷ represents an alkyl group of 1 to 6 carbonatoms, or a phenyl group; R²⁸ represents an alkyl group of 1 to 10carbon atoms or an aralkyl group of 1 to 10 carbon atoms; and d, e, andf independently represent an integer that satisfies the followingformulae: 8≧d≧0, 10≧e≧2, 8≧f≧0, and 10≧d+e+f≧3).

These compounds may be used alone or in combination. In particular, interms of the compatibility with (meth)acrylic polymers, linear siloxaneshaving phenyl groups represented by general formula (25) or (26), andcyclosiloxanes having phenyl groups represented by general formula (27)or (28) are preferable:(CH₃)₃SiO—[Si(H)(CH₃)O]_(g)—[Si(C₆H₅)₂O]_(h)—Si(CH₃)₃  (25)(CH₃)₃SiO—[Si(H)(CH₃)O]_(g)—[Si(CH₃){CH₂C(H)(R²⁴)C₆H₅}O]_(h)—Si(CH₃)₃  (26)(wherein R²⁴ represents a hydrogen atom or a methyl group, g and hindependently represent an integer that satisfies the followingformulae: 100≧g≧2 and 100≧h≧0, and C₆H₅ represents a phenyl group):

(wherein R²⁹ represents a hydrogen atom or a methyl group, i and jindependently represent an integer that satisfies the followingformulae: 10≧i≧2, 8≧j≧0, and 10≧a≧+j≧3, and C₆H₅ represents a phenylgroup).

The compounds (B) having at least 1.1 hydrosilyl groups per moleculefurther include compounds produced by addition reaction of compoundshaving hydrosilyl groups represented by general formulae (22) to (28)and low molecular compounds having at least two alkenyl groups permolecule, the addition reaction being performed so that the hydrosilylgroups partly remain after the reaction. Various compounds having atleast two alkenyl groups per molecule may be used. Examples of thecompounds having at least two alkenyl groups include hydrocarbons suchas 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene,1,8-nonadiene, and 1,9-decadiene; ethers such as O,O′-diallyl bisphenolA and 3,3-diallyl bisphenol A; esters such as diallyl phthalate, diallylisophthalate, triallyl trimellitate, and tetraallyl pyromellitate; andcarbonates such as diethylene glycol diallyl carbonate.

The above compounds having alkenyl groups are added dropwise slowly toan excess of the compounds having hydrosilyl groups represented bygeneral formulae (22) to (28) in the presence of a hydrosilylationcatalyst to produce the compound having hydrosilyl groups. In terms ofthe availability of raw materials, the ease to remove the excess ofsiloxane used, and the compatibility with the vinyl polymer, thefollowing compounds are preferable:

(wherein n represents an integer of 2 to 4 and m represents an integerof 5 to 10).

The vinyl polymers (A) and the compounds (B) having hydrosilyl groupsmay be mixed at any ratio. However, in terms of the curing ability, themolar ratio of the alkenyl group to the hydrosilyl group is preferably 5to 0.2 and more preferably 2.5 to 0.4. When the molar ratio exceeds 5,the cured material is sticky and has poor strength because ofinsufficient curing. On the other hand, when the molar ratio is lessthan 0.2, a large amount of the active hydrosilyl group remains in thecured material even after curing. Accordingly, the cured material hascracks and voids and is not uniform, and the cured material has poorstrength.

The curing reaction of the vinyl polymers (A) and the compounds havinghydrosilyl groups (B) proceeds by mixing and heating the two components.In order to promote the reaction, a hydrosilylation catalyst may beadded. The hydrosilylation catalyst is not limited. Examples of thehydrosilylation catalyst include radical initiators such as organicperoxides and azo compounds; and transition metal catalysts.

The radical initiator is not limited. Examples of the radical initiatorinclude dialkyl peroxides such as di-tert-butyl peroxide,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane,2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, dicumyl peroxide,tert-butylcumyl peroxide, andα,α′-bis(tert-butylperoxy)isopropylbenzene; diacyl peroxides such asbenzoyl peroxide, p-chlorobenzoyl peroxide, m-chlorobenzoyl peroxide,2,4-dichlorobenzoyl peroxide, and lauroyl peroxide; peracid esters suchas tert-butyl perbenzoate; peroxydicarbonates such as diisopropylperoxydicarbonate; and di-2-ethylhexyl peroxydicarbonate; andperoxyketals such as 1,1-di-(tert-butylperoxy)cyclohexane and1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane.

The transition metal catalysts are also not limited. Examples of thetransition metal catalysts include catalysts wherein solid platinum isdispersed on a carrier of elemental platinum, alumina, silica, or carbonblack; chloroplatinic acid; complexes of chloroplatinic acid withalcohols, aldehydes, or ketones; platinum-olefin complexes; and platinum(0)-divinyl tetramethyl disiloxane complex. Examples of the catalystother than platinum compounds include RhCl(PPh₃)₃, RhCl₃, RuCl₃, IrCl₃,FeCl₃, AlCl₃, PdCl₂.H₂O, NiCl₂, and TiCl₄. These catalysts may be usedalone or in combination. Although the content of the catalyst is notlimited, the content of the catalyst is preferably 10⁻¹ to 10⁻⁸ moles,preferably, 10⁻³ to 10⁻⁶ moles to one mole of the alkenyl group in thevinyl polymers (A). When the content of the catalyst is less than 10⁻⁸moles, the curing does not proceed sufficiently. The hydrosilylationcatalysts are generally expensive and corrosive; furthermore, a largeamount of hydrogen gas is generated to cause undesirable foaming of thecured material. Accordingly, the content of the catalyst is preferablyless than 10⁻¹ moles.

Although the curing temperature is not limited, the curing temperatureis generally 0° C. to 200° C., preferably, 30° C. to 150° C., and morepreferably, 80° C. to 150° C. The cured material can be formed in ashort time in this temperature range.

<Reactive Composition Susceptible to Hydrosilylation (2)>

The compounds (B) having hydrosilyl groups may be hydrosilane compoundshaving crosslinkable silyl groups.

The hydrosilane compounds having crosslinkable silyl groups are notlimited. Typical hydrosilane compounds having crosslinkable silyl groupsare represented by general formula (29):H—[Si(R¹¹)_(2-b)(Y)_(b)O]_(m)—Si(R¹²)_(3-a)(Y)_(a)  (29){wherein, each of R¹¹ and R¹² represents an alkyl group of 1 to 20carbon atoms, an aryl group of 6 to 20 carbon atoms, an aralkyl group of7 to 20 carbon atoms, or a triorganosiloxy group represented by(R′)₃SiO— (wherein R′ represents a monovalent hydrocarbon group of 1 to20 carbon atoms and the three R′s may be the same or different); whenthe number of R¹¹s or R¹²s is two or more, R¹¹s and R¹²s may be the sameor different; Y represents a hydroxyl group or a hydrolyzable group;when the number of Ys is two or more, Ys may be the same or different; arepresents 0, 1, 2, or 3, b represents 0, 1, or 2, and m represents aninteger of 0 to 19, wherein a+mb≧1)}.

Examples of the hydrolyzable group include hydrolyzable groups generallyused such as, a hydrogen atom, alkoxy groups, acyloxy groups, ketoximategroups, an amino group, an amido group, an aminooxy group, a mercaptogroup, and alkenyloxy groups. Among these groups, alkoxy groups, anamido group, and an aminooxy group are preferable. In terms of easyhandling due to mild hydrolyzability, alkoxy groups are particularlypreferable.

The number of the hydrolyzable groups or the hydroxyl groups that can bebonded with one silicon atom is 1 to 3, and the number represented by aformula (a+Σb) is preferably 1 to 5. When the number of the hydrolyzablegroups or the hydroxyl groups that are bonded with the crosslinkablesilyl groups is two or more, the hydrolyzable groups or the hydroxylgroups may be the same or different. The number of silicon atoms thatform the crosslinkable silyl groups is one or more. However, when thesilicon atoms are connected through, for example, siloxane bonds, thenumber of the silicon atoms is preferably 20 or less.

Among these hydrosilane compounds, compounds having a crosslinkablegroup represented by general formula (30):H—Si(R¹²)_(3-a)(Y)_(a)  (30)(wherein R¹², Y, and a are as defined above)are particularly preferable, in terms of the availability.

Reactive compositions susceptible to hydrosilylation containing theabove hydrosilane compounds (B) are subjected to hydrosilylation toproduce vinyl polymers having crosslinkable silyl groups.

Vinyl polymers having at least 1.1 crosslinkable silyl groups permolecule are crosslinked and form cured materials. The present inventionalso provides the vinyl polymers having at least 1.1 crosslinkable silylgroups per molecule produced by the above method, and the curablecompositions containing the vinyl polymers (curable composition (2)).

Examples of the crosslinkable silyl groups according to the presentinvention are represented by general formula (31):—[Si(R¹¹)_(2-b)(Y)_(b)O]_(m)—Si(R¹²)_(3-a)(Y)_(a)  (31){wherein, each of R¹¹ and R¹² represents an alkyl group of 1 to 20carbon atoms, an aryl group of 6 to 20 carbon atoms, or an aralkyl groupof 7 to 20 carbon atoms or a triorganosiloxy group represented by(R′)₃SiO— (wherein R′ represents a monovalent hydrocarbon group of 1 to20 carbon atoms and the three R′s may be the same or different); whenthe number of R′s or R¹²s is two or more, R¹¹s and R¹²s may be the sameor different; Y represents a hydroxyl group or a hydrolyzable group;when the number of Ys is two or more, Ys may be the same or different; arepresents 0, 1, 2, or 3, b represents 0, 1, or 2, and m represents aninteger of 0 to 19, wherein a+mb≧1)}.

Examples of the hydrolyzable group include hydrolyzable groups generallyused such as, a hydrogen atom, alkoxy groups, acyloxy groups, ketoximategroups, an amino group, an amido group, an aminooxy group, a mercaptogroup, and alkenyloxy groups. Among these groups, alkoxy groups, anamido group, and an aminooxy group are preferable. In terms of easyhandling due to mild hydrolyzability, alkoxy groups are particularlypreferable.

The number of the hydrolyzable groups or the hydroxyl groups that can bebonded with one silicon atom is 1 to 3, and the number represented by aformula (a+Σb) is preferably 1 to 5. When the number of the hydrolyzablegroups or the hydroxyl groups that are bonded with the crosslinkablesilyl groups is two or more, the hydrolyzable groups or the hydroxylgroups may be the same or different. The number of silicon atoms thatform the crosslinkable silyl groups is one or more. However, when thesilicon atoms are connected through, for example, siloxane bonds, thenumber of the silicon atoms is preferably 20 or less. In particular,crosslinkable silyl groups represented by general formula (32):—Si(R¹²)_(3-a)(Y)_(a)  (32)(wherein R¹⁰, Y, and a are as defined above)are preferable, in terms of the availability.

If the cured material produced by curing the vinyl polymer havingcrosslinkable silyl groups according to the present invention especiallyrequires an elastic property, at least one of the crosslinkable silylgroups is preferably located at one end of the molecular chain becausethis molecular chain structure can increase the molecular weight betweencrosslinks that greatly effects on the rubber elasticity. Morepreferably, the vinyl polymer includes all the functional groups at theends of the molecular chain.

Although the ratio of the vinyl polymers (A) to the hydrosilanecompounds (B) having crosslinkable silyl groups is not limited, thecontent of the hydrosilyl groups is preferably equivalent or more of thecontent of the alkenyl groups.

In order to promote hydrosilylation, a hydrosilylation catalyst may beadded. Any hydrosilylation catalyst described above may be used.

Although the reaction temperature is not limited, the reactiontemperature is generally 0° C. to 200° C., preferably, 30° C. to 150°C., and more preferably, 80° C. to 150° C.

When the curable composition (2) is cured, a condensation catalyst maybe used or not. Examples of the condensation catalyst include titanatessuch as tetrabutyl titanate and tetrapropyl titanate; organotincompounds such as dibutyltin dilaurate, dibutyltin diacetylacetonate,dibutyltin maleate, dibutyltin diacetate, dibutyltin dimethoxide, tinoctylate, and tin naphthenate; lead octylate; amines or the carboxylatesthereof such as butylamine, octylamine, dibutylamine, monoethanolamine,diethanolamine, triethanolamine, diethylenetriamine,triethylenetetramine, oleylamine, octylamine, cyclohexylamine,benzylamine, diethylaminopropylamine, xylylenediamine,triethylenediamine, guanidine, diphenylguanidine,2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine,and 1,3-diazabicyclo(5,4,6)undecene-7; reaction products and mixtures ofamines and organotin compounds such as reaction product and mixture oflaurylamine and tin octylate; low molecular weight polyamide resinsproduced from an excess polyamine and a polybasic acid; reactionproducts of an excess polyamine and an epoxy compound; and silanecoupling agents having amino groups, for example,γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)aminopropylmethyldimethoxysilane. If necessary, at least one of theseknown silanol catalysts may be used. The content of the catalyst ispreferably 0 to 10 weight percent of the vinyl polymer havingcrosslinkable terminal silyl groups. When the hydrolyzable group Y is analkoxy group, the curing rate of the polymers is low. Accordingly, thecuring catalyst is preferably added.

<Curable Composition>

In order to control the physical properties, if necessary, variousadditives may be appropriately mixed with the above curable composition(1) and curable composition (2). Examples of the additives include flameretardants, age resisters, fillers, plasticizers, physical-propertymodifiers, reactive diluents, adhesive agents (i.e., adhesion-impartingagents), storage stability improvers, solvents, radical inhibitors,metal deactivators, antiozonants, phosphorus peroxide decomposers,lubricants, pigments, foaming agents, and photocurable resins. Theseadditives may be used alone or in combination.

Since vinyl polymers originally have superior durability, the ageresisters are not always necessary. However, known additives such asantioxidants, ultraviolet absorbers, and light stabilizers may beappropriately added.

<Fillers>

Any filler may be mixed. In order to improve a physical property such asstrength, examples of reinforcing filler include silica particles,calcium carbonate, talc, titanium oxide, diatomaceous earth, bariumsulfate, carbon black, surface treated fine calcium carbonate, firedclay, clay, and active zinc flower. These reinforcing fillers may beused alone or in combination. Among these reinforcing fillers, silicaparticles are preferable. Examples of the silica particles includehydrated silica produced by a wet process and dry-process silicaproduced by a dry process. In particular, silica anhydride is preferablyadded because large water content in the compositions may cause, forexample, side reaction during the curing reaction. Silica anhydridewhose surface is subjected to hydrophobic treatment is more preferablyadded because the composition has appropriate fluidity during molding.Furthermore, fillers having low reinforcing property may be used inorder to increase the weight or to adjust the physical property.

<Plasticizer>

Any plasticizer may be mixed. In order to modify the physical propertyand to control the appearance, examples of the plasticizer includephthalate esters such as dibutylphthalate, diheptylphthalate,di(2-ethylhexyl)phthalate, and butylbenzylphthalate; nonaromatic dibasicacid esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate,and isodecyl succinate; aliphatic esters such as butyl oleate and methylacetyl ricinoleate; polyalkyleneglycol esters such as diethyleneglycoldibenzoate, triethyleneglycol dibenzoate, and pentaerythritol esters;phosphoric esters such as tricresyl phosphate and tributyl phosphate;trimellitates; polystyrenes such as polystyrene andpoly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene,butadiene-acrylonitrile, polychloroprene; chlorinated paraffins;hydrocarbon oils such as alkyldiphenyl and hydrogenated terphenyl;process oils; polyethers such as polyetherpolyols, e.g. polyethyleneglycol, polypropylene glycol and polytetramethylene glycol, andderivatives produced by replacing the hydroxyl groups of thepolyetherpolyols with, for example, ester groups and ether groups; epoxyplasticizer such as epoxydized soybean oil and benzyl epoxystearate;polyester plasticizers derived from dibasic acids (e.g. sebacic acid,adipic acid, azelaic acid, and phthalic acid) and dihydric alcohols(e.g. ethylene glycol, diethylene glycol, triethylene glycol, propyleneglycol, and dipropylene glycol); and vinyl polymers produced bypolymerizing vinyl monomers such as acrylic plasticizer using variousmethods. Although these plasticizers may be used alone or incombination, the plasticizers are not always necessary. Theseplasticizers may be mixed during producing the polymers.

<Storage Stability Improvers>

Any storage stability improvers may be mixed. The storage stabilityimprovers suppress the increase in viscosity during storage of thecomposition, and suppress a significant change in the curing rate afterstorage of the composition. Examples of the storage stability improverinclude benzothiazole and dimethyl maleate.

<Solvents>

Examples of the solvents include aromatic hydrocarbons such as tolueneand xylenes; esters such as ethyl acetate, butyl acetate, amyl acetate,and cellosolve acetate; and ketones such as methyl ethyl ketone, methylisobutyl ketone, and diisobutyl ketone. These solvents may be usedduring producing the polymers.

<Adhesive Agents>

Any adhesive agents (i.e., adhesion-imparting agents) that provide thecured materials with adhesiveness may be used. Compounds havingcrosslinkable silyl groups are preferable, and silane coupling agentsare more preferable. Examples of the silane coupling agent includealkylalkoxysilanes such as methyltrimethoxysilane,dimethyldimethoxysilane, trimethylmethoxysilane, andn-propyltrimethoxysilane; alkylisopropenoxy silanes such asdimethyldiisopropenoxy silane and methyltriisopropenoxy silane; silaneshaving vinyl unsaturated groups such as vinyltrimethoxysilane,vinyldimethylmethoxysilane, vinyltriethoxysilane,γ-methacryloyloxypropyl methyldimethoxysilane, and γ-acryloyloxypropylmethyltriethoxysilane; silicone varnishes; and polysiloxanes.

In particular, preferable silane coupling agents include organic groupsthat include atoms other than a carbon atom and a hydrogen atom (e.g.epoxy, (meth)acrylic, isocyanate, isosyanurate, carbamate, amino,mercapto, and carboxyl groups) and crosslinkable silyl groups. Examplesof alkoxy silanes having an isocyanate group include silanes having anisocyanate group such as γ-isocyanatopropyltrimethoxysilane,γ-isocyanatopropyltriethoxysilane,γ-isocyanatopropylmethyldiethoxysilane, andγ-isocyanatopropylmethyldimethoxysilane. Examples of alkoxy silaneshaving isocyanurate groups include isocyanurate silanes such astris(trimethoxysilyl)isocyanurate. Examples of alkoxy silanes havingamino groups include silanes having an amino group such asγ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane,N-(β-amonoethyl)-γ-aminopropyltrimethoxysilane,N-(β-amonoethyl)-γ-aminopropylmethyldimethoxysilane,N-(β-amonoethyl)-γ-aminopropyltriethoxysilane,N-(β-amonoethyl)-γ-aminopropylmethyldiethoxysilane,γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane,N-benzyl-γ-aminopropyltrimethoxysilane, andN-vinylbenzyl-γ-aminopropyltriethoxysilane. Examples of alkoxy silaneshaving a mercapto group include silanes having a mercapto group such asγ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane,γ-mercaptopropylmethyldimethoxysilane, andγ-mercaptopropylmethyldiethoxysilane. Examples of alkoxy silanes havinga carboxyl group include carboxy silanes such asβ-carboxyethyltriethoxysilane,β-carboxyethylphenylbis(2-methoxyethoxy)silane, andN-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane. Examples ofalkoxy silanes having a halogen group include silanes having a halogensuch as γ-chloropropyltrimethoxysilane.

Modified derivatives such as amino-modified silyl polymers, silylatedamino polymers, unsaturated aminosilane complexes, phenylaminolong-chain alkylsilanes, aminosilylated silicones, and silylatedpolyesters may be also used as the silane coupling agents.

Furthermore, in terms of curing ability and adhesive property, alkoxysilanes having epoxy or (meth)acrylic groups are more preferable.Examples of the alkoxy silanes having an epoxy group includeγ-glycidoxypropylmethyldimethoxysilane,γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,β-(3,4-epoxycyclohexy) ethyltrimethoxysilane, β-(3,4-epoxycyclohexy)ethyltriethoxysilane, and γ-glycidoxypropylmethyldiisopropenoxysilane.Examples of the alkoxy silanes having a (meth)acrylic group includeγ-methacryloxypropyltrimethoxysilane,γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane,γ-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane,methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, andacryloxymethyltriethoxysilane. These alkoxy silanes may be used alone orin combination.

In order to further improve the adhesive property, catalysts forcondensing the crosslinkable silyl group may be used with the adhesiveagents. Examples of the catalysts for condensing the crosslinkable silylgroup include organotin compounds such as dibutyltin dilaurate,dibutyltin diacetylacetonate, dibutyltin dimethoxide, and tin octylate;organoaluminum compounds such as aluminum acetylacetonate;organotitanium compounds such as tetraisopropoxy titanium andtetrabutoxy titanium.

Examples of the adhesive agent other than the silane coupling agents arenot limited. Examples of the adhesive agent include epoxy resin, phenolresin, sulfur, alkyl titanates, and aromatic polyisocyanates.

The content of the adhesive agents is preferably 0.01 to 20 parts byweight to 100 parts by weight of the vinyl polymer. When the content ofthe adhesive agents is less than 0.01 parts by weight, the improvementof the adhesive properties is not sufficient. When the content of theadhesive agents exceeds 20 parts by weight, the physical properties ofthe cured material are poor. The content of the adhesive agents is morepreferably 0.1 to 10 parts by weight, and most preferably, 0.5 to 5parts by weight.

The adhesive agents may be used alone or in combination. Adding theseadhesive agents improves the adhesive property to adherends.

<Molding Processes>

The reactive compositions susceptible to hydrosilylation of the presentinvention may be used for general molding processes to produce moldedarticles. Examples of the molding process include casting, compressionmolding, transfer molding, injection molding, extrusion molding,rotational molding, blow molding, and thermoforming. In particular,injection molding is preferable due to high productivity by automationand a continuous process. When the reactive compositions susceptible tohydrosilylation are used as gaskets, both wet type and dry type areavailable. In the wet type, an uncured reactive composition susceptibleto hydrosilylation is applied on, for example, a flange face and bothsides of the flanges are pinched, and then the reactive composition iscured. In the dry type, the reactive composition susceptible tohydrosilylation is cured, and then both sides are pinched.

<Applications>

Applications of the reactive compositions susceptible to hydrosilylationof the present invention are not limited. Examples of applicationsinclude sealants such as architectural elastic sealants and sealantsused for double glazing; electrical and electronic components such assealants used for the rear-side of solar cells; electrical insulatingmaterials such as insulating coating materials used for electrical wiresand cables; adhesives; bonds; elastic bonds; paints; powdered paints;coating materials; foams; potting materials used for electrical andelectronic components; films; gaskets; casting materials; syntheticmarble; molding materials; and antirust and waterproof sealants used forend faces (cut sections) of wire glasses and laminated glasses.

Furthermore, molded articles having rubber elasticity produced from thereactive compositions susceptible to hydrosilylation of the presentinvention can be widely used as mainly, for example, gaskets andpackings. For example, in the automobile field, the molded articlesproduced from the reactive compositions susceptible to hydrosilylationof the present invention can be used as body parts such as sealants tomaintain air tightness, vibration isolating materials for glass,vibration isolating materials for automobile bodies, and in particular,gaskets used for windshields, and gaskets used for door glasses. Themolded articles can be used as automobile chassis parts such asvibration-proof and soundproof engines, suspension rubbers, and inparticular, engine mount rubbers. The molded articles can be used asengine parts such as hoses used for, e.g., cooling, fuel supply, andexhaust control; and sealants for engine oils. Furthermore, the moldedarticles can also be used as parts of purifying equipment of exhaust gasand brake parts. In the household electric appliances field, the moldedarticles can be used as packings, O-rings, and belts. Specifically,examples of the molded articles used in lighting equipment includeornaments, waterproof packings, rubber vibration isolators, andinsect-proof packings. Examples of the molded articles used in a cleanerinclude a vibration isolating material, a sound absorption material, andan air sealant. Examples of the molded articles used in an electricwater heater include a drip-proof cover, a waterproof packing, a heaterpacking, an electrode packing, and a diaphragm used for a safety valve.Examples of the molded articles used in a sake warmer (i.e., rice winewarmer) include hoses, a waterproof packing, and an electromagneticvalve. Examples of the molded articles used in a steam oven, a range anda jar rice cooker include a waterproof packing, a packing used for afeed water tank, a suction valve, a packing used for a water receiver, aconnecting hose, a belt, a heater packing, oil packings for a burningappliance such as a seal of a steam outlet hole, an O-ring, a drainpacking, a pressure tube, a blower tube, a packing used for air supplyand intake air, a rubber vibration isolator, a packing used for an oilsupply port, a packing used for an oil level indicator, an oil feedpipe, a diaphragm valve, and an air supply tube. Examples of the moldedarticles used in an acoustic instrument include a speaker gasket, aspeaker edge, a turntable sheet, a belt, and a pulley. In thearchitectural field, the molded articles can be used as, for example, astructural gasket (zipper gasket), a roofing material having a pneumaticstructure, a waterproof material, a preformed sealant, a vibrationisolating material, a soundproof material, a setting block, and asliding material. In the sports field, the molded articles can be usedas, for example, floor materials for sports, such as a surface materialfor all weather facilities, a floor material for a gymnasium; sportsshoes such as a shoe sole material and an inner sole material; and ballsfor ball games such as golf balls. In the rubber vibration insulatorfield, the molded articles can be used as, for example, rubber vibrationinsulators used for automobiles, rubber vibration insulators used forrailroad vehicles, rubber vibration insulators used for aircrafts, andfender materials. In the ocean and civil engineering field, the moldedarticles can be used as structural materials such as a rubber expansionjoint, a bearing, a water stop, a waterproof sheet, a rubber dam, anelastic pavement, a vibration-absorbing pad, and a protector;submaterials for construction such as a rubber molding flask, a rubberpacker, a rubber skirt, a sponge mat, a mortar hose, and a mortarstrainer; auxiliary materials for construction such as rubber sheets andan air hose; commodities for safety measures such as a rubber buoy and amaterial for wave dissipation; and commodities for environmentalprotection such as an oil boom, a silt fence, an antifouling material, amarine hose, a dredging hose, and an oil skimmer. Furthermore, themolded articles can also be used as, for example, a rubber plate, a mat,and a foam plate.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will now be further described with reference tothe following non-limiting examples in detail.

(Measurement of the Number Average Molecular Weight and Molecular WeightDistribution)

The number average molecular weight and the molecular weightdistribution (the ratio of the weight average molecular weight to thenumber average molecular weight) were determined by gel permeationchromatography (GPC) with a polystyrene standard. The GPC columns usedwere filled with crosslinked polystyrene gel (Shodex GPC K-804 andK-8025; SHOWA DENKO K.K.) and the GPC solvent used was chloroform.

(Average Number of Functional Groups)

The average number of functional groups was calculated by ¹H NMR(nuclear magnetic resonance) analysis and the number average molecularweight that was determined by GPC.

(Curing Test)

A polymer and a solution of xylene containing a linear siloxane (thelinear siloxane includes five hydrosilyl groups on average and fivesubstituents [—CH₂—CH(CH₃)—C₆H₅] on average per molecule, and the amountof Si—H group was 3.70 mmol/g) and1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zero-valentplatinum (content of the platinum: 1.3×10⁻⁵ mmol/μL) were mixed manuallyto prepare a composition. The content of the linear siloxane wascontrolled so that the molar ratio of the alkenyl groups to thehydrosilyl groups was 1/1.5. The amount of platinum catalyst wasrepresented by the molar ratio relative to the alkenyl groups. Afraction of the composition was heated on a hotplate at 130° C. withstirring in air to measure the gelation time.

(Measurement of Copper Content)

Ultrapure nitric acid and ultrapure sulfuric acid were mixed with thepolymer to degrade the polymer by microwave treatment. The residualcopper content in the degraded product was measured by an inductivelycoupled plasma mass spectrometer (ICP-MS) (HP-4500, Yokogawa AnalyticalSystems Inc.) to determine the residual copper content in the polymer.

Manufacturing Example 1 Method for Producing a Vinyl Polymer havingTerminal Alkenyl Groups

In a 250-L reactor having a stirrer and a jacket, CuBr (1,740 g) wascharged and the atmosphere in the reactor was replaced with nitrogen.Acetonitrile (13.5 kg) was added, hot water was supplied through thejacket, and the mixture was stirred for 30 minutes at 80° C. Butylacrylate (212 kg) and diethyl 2,5-dibromoadipate (3,692 g) were addedand the mixture was further stirred for 25 minutes at 80° C.Pentamethyldiethylenetriamine (herein after referred to as triamine)(60.7 g) was added to the mixture to initiate the reaction. Triamine(961 g) was appropriately added to the mixture during the reaction.After 8 hours from the initiation of the reaction, 1,7-octadiene (16.5kg) and triamine (607 g) were added to the mixture and the mixture wasstirred for 6 hours.

The polymer solution was heated at 100° C. under reduced pressure toevaporate acetonitrile and 1,7-octadiene. Then the residue was dissolvedin the same weight of toluene.

A hydrotalcite adsorbent (2 parts by weight; Kyowaad 500SH, KyowaChemical Industry Co., Ltd.) and aluminum silicate (i.e., adsorbent) (2parts by weight: Kyowaad 700SL, Kyowa Chemical Industry Co., Ltd.) wereadded to the solution containing 100 parts by weight of the polymer. Thepolymer solution was heated at 100° C. for 2 hours. The solution wassubjected to solid-liquid separation with a de Laval type centrifuge(12,800 G, residence time: 2 minutes) to remove solid copper and theadsorbents. Furthermore, the hydrotalcite adsorbent (2 parts by weight;Kyowaad 500SH, Kyowa Chemical Industry Co., Ltd.) and aluminum silicate(2 parts by weight; Kyowaad 700SL, Kyowa Chemical Industry Co., Ltd.)were added to the polymer solution containing 100 parts by weight of thepolymer. The polymer solution was heated at 100° C. for 2 hours. Thesolution was subjected to solid-liquid separation with the de Laval typecentrifuge (12,800 G, residence time: 2 minutes). The polymer solutionwas heated under reduced pressure at 80° C. to evaporate toluene.

The resultant polymer (50 kg) and potassium acetate (725 g) were chargedin a 250-L reactor. N,N-dimethylacetamide (hereinafter referred to asDMAC) (58 kg) was added to the mixture and the mixture was stirred at100° C. for 8 hours under nitrogen atmosphere. DMAC in the mixture wasevaporated under reduced pressure at 100° C. to recover a polymer thatdoes not have a bromine group. The number average molecular weight ofthe polymer was 28,801, the molecular weight distribution of the polymerwas 1.36, and the average number of alkenyl groups introduced per onepolymer molecule was 2.83. The copper content in the polymer was 243 ppmby weight. According to the curing test of this polymer, when thecontent of the platinum catalyst was 0.008 equivalents, the curing timewas 30 seconds.

In a 250-L reactor having a stirrer and a jacket, the above polymer(48.89 kg) was charged. The hydrotalcite adsorbent (969 g; Kyowaad500SH, Kyowa Chemical Industry Co., Ltd.) and aluminum silicate (969 g;Kyowaad 700SL, Kyowa Chemical Industry Co., Ltd.) were added, and thenthe atmosphere in the reactor was replaced with nitrogen. The mixturewas stirred at 150° C. for 5 hours to recover Polymer [1].

Polymer [1] was diluted with the same weight of toluene, and theadsorbents were removed by ultracentrifugation (9,100 G, processingtime: 2 minutes). The resultant clear solution was condensed to recoverthe polymer. The copper content in the polymer was 33 ppm by weight.According to the curing test of this polymer, when the content of theplatinum catalyst was 0.0016 equivalents, the curing time was 30seconds.

EXAMPLE 1

Polymer [1] (about 50 g) produced by Manufacturing Example 1, i.e.,Polymer [1] containing the adsorbents was charged in a 500-mL separableflask and was heated at 150° C. for 1 hour in air. Subsequently, theresultant polymer was diluted with the same weight of toluene, and theadsorbents were removed by ultracentrifugation (9,100 G, processingtime: 2 minutes). The resultant clear solution was condensed to recoverthe polymer. According to the curing test of this polymer, when thecontent of the platinum catalyst was 0.0007 equivalents, the curing timewas 30 seconds.

Manufacturing Example 2 Method for Producing a Vinyl Polymer havingTerminal Alkenyl Groups

In a 250-L reactor having a stirrer and a jacket, CuBr (1.41 kg) wascharged and the atmosphere in the reactor was replaced with nitrogen.Acetonitrile (12.63 kg) was added, hot water was supplied through thejacket, and the mixture was stirred for 30 minutes at 80° C. Butylacrylate (42.00 kg), ethyl acrylate (60.37 kg), methoxyethyl acrylate(49.00 kg), and diethyl 2,5-dibromoadipate (3.93 kg) were added and themixture was further stirred for 25 minutes at 80° C. Triamine (56.8 g)was added to the mixture to initiate the reaction. During the reaction,triamine (56.8 g) was further added five times to the mixture (284.0 gin total). After 6 hours from the initiation of the reaction,1,7-octadiene (36.11 kg) and triamine (568 g) were added to the mixtureand the mixture was stirred for 6 hours.

The reaction mixture (145 kg) was diluted with toluene (91 kg). Themixture was subjected to solid-liquid separation with a de Laval typecentrifuge (12,800 G, residence time: 2 minutes).

The polymer solution was heated under reduced pressure at 100° C. toevaporate acetonitrile, 1,7-octadiene, and toluene. Then the resultantpolymer (106 kg) was dissolved in toluene (100 kg). A hydrotalciteadsorbent (2 parts by weight; Kyowaad 500SH, Kyowa Chemical IndustryCo., Ltd.) and aluminum silicate (2 parts by weight; Kyowaad 700SL,Kyowa Chemical Industry Co., Ltd.) were added to the solution containing100 parts by weight of the polymer. The polymer solution was heated at100° C. for 2 hours. The solution was subjected to solid-liquidseparation with the de Laval type centrifuge (12,800 G, residence time:2 minutes) to remove solid copper and the adsorbents. The polymersolution was heated under reduced pressure at 80° C. to evaporatetoluene.

The resultant polymer (96 kg) and potassium acetate (2,184 g) werecharged in a 250-L reactor. DMAC (90 kg) was added to the mixture andthe mixture was stirred at 100° C. for 8 hours under nitrogenatmosphere. The mixture was heated under reduced pressure at 100° C. toevaporate DMAC to recover a polymer (Polymer [2]) that does not have abromine group.

The number average molecular weight of Polymer [2] was 17,802, themolecular weight distribution of Polymer [2] was 1.18, and the averagenumber of alkenyl groups introduced per one polymer molecule was 2.14.The copper content in the polymer was 171 ppm by weight. According tothe curing test of this polymer, when the content of the platinumcatalyst was 0.009 equivalents, the curing time was 30 seconds.

EXAMPLE 2

Polymer [2] (about 50 g) produced by Manufacturing Example 2 was chargedin a 500-mL separable flask, and a hydrotalcite adsorbent (1 g; Kyowaad500SH, Kyowa Chemical Industry Co., Ltd.) and aluminum silicate (1 g;Kyowaad 700SL, Kyowa Chemical Industry Co., Ltd.) were added to thepolymer. Subsequently the mixture was stirred at 130° C. for 5 hours inair to prepare a polymer. The resultant polymer was diluted with thesame weight of toluene and the adsorbents were removed byultracentrifugation (9,100 G, processing time: 2 minutes). The resultantclear solution was condensed to recover the polymer. The copper contentin the polymer was 21 ppm by weight. According to the curing test ofthis polymer, when the content of the platinum catalyst was 0.0006equivalents, the curing time was 29 seconds.

Comparative Example 1

Polymer [2] (about 50 g) produced by Manufacturing Example 2 was chargedin a 500-mL separable flask, and a hydrotalcite adsorbent (1 g; Kyowaad500SH, Kyowa Chemical Industry Co., Ltd.) and aluminum silicate (1 g;Kyowaad 700SL, Kyowa Chemical Industry Co., Ltd.) were added to thepolymer. Subsequently the atmosphere was replaced with nitrogen and themixture was stirred at 130° C. for 5 hour to prepare a polymer. Theresultant polymer was diluted with the same weight of toluene and theadsorbents were removed by ultracentrifugation (9,100 G, processingtime: 2 minutes). The resultant clear solution was condensed to recoverthe polymer. The copper content in the polymer was 16 ppm by weight.According to the curing test of this polymer, when the content of theplatinum catalyst was 0.002 equivalents, the curing time was 35 seconds.

According to the results of Example 2 and Comparative Example 1, whenthe treatment with the adsorbent was performed in an oxygen-containingatmosphere, the hydrosilylation proceeded with smaller amount ofplatinum catalyst, compared with the treatment with the adsorbentperformed in nitrogen. Thus, the hydrosilylation activity of the polymerwas significantly improved. Furthermore, the treatment with theadsorbent in an oxygen-containing atmosphere decreases the coppercontent, compared with the treatment with the adsorbent performed innitrogen.

Manufacturing Example 3 Method for Producing a Vinyl Polymer HavingTerminal Alkenyl Groups

In a 250-L reactor having a stirrer and a jacket, CuBr (1.11 kg) wascharged and the atmosphere in the reactor was replaced with nitrogen.Acetonitrile (29.87 kg) was added, hot water was supplied through thejacket, and the mixture was stirred for 30 minutes at 80° C. Butylacrylate (33.00 kg), ethyl acrylate (47.43 kg), methoxyethyl acrylate(38.87 kg), and diethyl 2,5-dibromoadipate (3.09 kg) were added and themixture was further stirred for 25 minutes at 80° C. Triamine (45 g) wasadded to the mixture to initiate the reaction. During the reaction,triamine (45 g) was further added four times to the mixture (180 g intotal). After 6 hours from the initiation of the reaction, theatmosphere in the reactor was deaerated under reduced pressure at 80° C.for 2 hours. 1,7-Octadiene (28.37 kg) and triamine (446 g) were added tothe mixture and the mixture was stirred for 6 hours.

The polymer solution was heated under reduced pressure at 80° C. toevaporate acetonitrile and 1,7-octadiene. Then the resultant polymer wasdissolved in the same weight of toluene.

The polymer solution was subjected to solid-liquid separation with a deLaval type centrifuge (12,800 G, residence time: 2 minutes). Ahydrotalcite adsorbent (2 parts by weight; Kyowaad 500SH, Kyowa ChemicalIndustry Co., Ltd.) and aluminum silicate (2 parts by weight; Kyowaad700SL, Kyowa Chemical Industry Co., Ltd.) were added to the polymersolution (199.4 kg) containing 100 parts by weight of the polymer. Thepolymer solution was heated at 120° C. for 6 hours. The solution wassubjected to solid-liquid separation with the de Laval type centrifuge(12,800 G, residence time: 2 minutes) to remove solid copper and theadsorbents. The polymer solution was heated under reduced pressure at100° C. to evaporate toluene.

The resultant polymer (73.4 kg) and potassium acetate (1,907 g) werecharged in a 250-L reactor. DMAC (73.4 kg) was added to the mixture andthe mixture was stirred at 100° C. for 8 hours under nitrogenatmosphere. The mixture was heated under reduced pressure at 100° C. toevaporate DMAC to recover a polymer (Polymer [3]) that does not have abromine group.

The number average molecular weight of Polymer [3] was 16,962, themolecular weight distribution of Polymer [3] was 1.23, and the averagenumber of alkenyl groups introduced per one polymer molecule was 1.60.The copper content in the polymer was 23 ppm by weight. According to thecuring test of this polymer, when the content of the platinum catalystwas 0.02 equivalents, the curing time was 150 seconds.

EXAMPLE 3

Polymer [3] (72.35 kg) produced by Manufacturing Example 3 was chargedin a 250-L reactor having a stirrer and a jacket, and a hydrotalciteadsorbent (3,600 g; Kyowaad 500SH, Kyowa Chemical Industry Co., Ltd.)and aluminum silicate (3,600 g; Kyowaad 700SL, Kyowa Chemical IndustryCo., Ltd.) were added to the polymer. Subsequently the mixture wasstirred at 130° C. for 5 hours in a gas phase containing 12.7% oxygen toprepare a polymer. The polymer was diluted with five times the weight oftoluene. A filter paper (4 μm) and a filter aid (Radiolite #300, ShowaChemical Industry Co., Ltd.) were disposed in a Kiriyama funnel (60 mmin diameter) to form a filter aid layer (5 mm in thickness). The polymersolution was filtrated under reduced pressure. Toluene in the filtratewas evaporated and the copper content in the polymer was measured. Thecopper content was 2 ppm by weight or less. According to the curing testof this polymer, when the content of the platinum catalyst was 0.0003equivalents, the curing time was 20 seconds.

Manufacturing Example 4 Method for Producing a Vinyl Polymer havingTerminal Alkenyl Groups

In a 250-L reactor having a stirrer and a jacket, CuBr (1.01 kg) wascharged and the atmosphere in the reactor was replaced with nitrogen.Acetonitrile (10.55 kg) was added, hot water was supplied through thejacket, and the mixture was stirred for 30 minutes at 80° C. Butylacrylate (120 kg) and diethyl 2,5-dibromoadipate (2.11 kg) were addedand the mixture was further stirred for 25 minutes at 80° C. Triamine(40.6 g) was added to the mixture to initiate the reaction. During thereaction, triamine (40.6 g) was further added four times to the mixture(162.4 g in total). After 6 hours from the initiation of the reaction,the atmosphere in the reactor was deaerated under reduced pressure at80° C. for 2 hours. 1,7-Octadiene (12.90 kg) and triamine (406 g) wereadded to the mixture and the mixture was stirred for 6 hours.

The polymer solution was heated under reduced pressure at 80° C. toevaporate acetonitrile and 1,7-octadiene. Then the resultant polymer wasdissolved in the same weight of toluene.

The polymer solution was subjected to solid-liquid separation with a deLaval type centrifuge (12,800 G, residence time: 2 minutes).

A hydrotalcite adsorbent (2 parts by weight; Kyowaad 500SH, KyowaChemical Industry Co., Ltd.) and aluminum silicate (2 parts by weight;Kyowaad 700SL, Kyowa Chemical Industry Co., Ltd.) were added to thepolymer solution containing 100 parts by weight of the polymer. Thepolymer solution was heated at 100° C. for 2 hours. The solution wassubjected to solid-liquid separation with the de Laval type centrifuge(12,800 G, residence time: 2 minutes) to remove solid copper. Thus, apolymer solution (Polymer solution [4′]) was recovered.

The polymer solution was condensed to recover the polymer (Polymer [4]).The number average molecular weight of Polymer [4] was 25,832, themolecular weight distribution of Polymer [4] was 1.26, and the averagenumber of alkenyl groups introduced per one polymer molecule was 1.77.The copper content in the polymer was 12 ppm by weight. According to thecuring test of this polymer, when the content of the platinum catalystwas 0.002 equivalents, the curing time was 30 seconds.

EXAMPLE 4

Polymer solution [4′] (about 43.3 kg) produced by Manufacturing Example4 was charged in a 100-mL autoclave, and a hydrotalcite adsorbent (0.433g; Kyowaad 500SH, Kyowa Chemical Industry Co., Ltd.) and aluminumsilicate (0.433 g; Kyowaad 700SL, Kyowa Chemical Industry Co., Ltd.)were added to the polymer solution. Subsequently the mixture was stirredat 150° C. for 1 hour in a gas phase containing 10% oxygen to prepare apolymer. The polymer was diluted with double the weight ofmethylcyclohexane. A filter paper (4 μm) and a filter aid (Radiolite#300, Showa Chemical Industry Co., Ltd.) were disposed in a Kiriyamafunnel (60 mm in diameter) to form a filter aid layer (5 mm inthickness). The polymer solution was filtrated under reduced pressure.Methylcyclohexane in the filtrate was evaporated and the copper contentin the polymer was measured. The copper content was 2 ppm by weight orless. According to the curing test of this polymer, when the content ofthe platinum catalyst was 0.0007 equivalents, the curing time was 36seconds.

Comparative Example 2

Polymer solution [4′] (about 43.3 g) produced by Manufacturing Example 4was charged in a 100-mL autoclave, and a hydrotalcite adsorbent (0.433g; Kyowaad 500SH, Kyowa Chemical Industry Co., Ltd.) and aluminumsilicate (0.433 g; Kyowaad 700SL, Kyowa Chemical Industry Co., Ltd.)were added to the polymer solution. Subsequently the atmosphere wasreplaced with nitrogen and the mixture was stirred at 150° C. for 1 hourto prepare a polymer. The polymer was diluted with double the weight ofmethylcyclohexane. A filter paper (4 μm) and a filter aid (Radiolite#300, Showa Chemical Industry Co., Ltd.) were disposed in a Kiriyamafunnel (60 mm in diameter) to form a filter aid layer (5 mm inthickness). The polymer solution was filtrated under reduced pressure.Methylcyclohexane in the filtrate was evaporated and the copper contentin the polymer was measured. The copper content was 2 ppm by weight orless. According to the curing test of this polymer, when the content ofthe platinum catalyst was 0.003 equivalents, the curing time was 36seconds.

According to the results of Example 4 and Comparative Example 2, whenthe treatment with the adsorbent was performed in an oxygen-containingatmosphere, the hydrosilylation proceeded with smaller amount ofplatinum catalyst, compared with the treatment with the adsorbentperformed in nitrogen. Thus, the hydrosilylation activity of the polymerwas significantly improved.

EXAMPLE 5

Polymer solution [4′] (990 g) produced by Manufacturing Example 4, ahydrotalcite adsorbent (9.9 g; Kyowaad 500SH, Kyowa Chemical IndustryCo., Ltd.), and aluminum silicate (9.9 g; Kyowaad 700SL, Kyowa ChemicalIndustry Co., Ltd.) were charged in a 2.8-L autoclave. Oxygenconcentration in the gas phase was measured with an oxygen gasconcentration meter. The oxygen concentration was 12.5%. (The gas phasecontained oxygen atoms of 0.51 molar ratio to the copper content.)Subsequently, the solution was heated at 150° C. and maintained at thetemperature for 1 hour. The polymer solution (about 100 g) was sampled,and then the oxygen concentration in the gas phase in the autoclave wasmeasured. The oxygen concentration was 4.8%. A filter paper (4 μm) and afilter aid (Radiolite #300, Showa Chemical Industry Co., Ltd.) weredisposed in a Kiriyama funnel (60 mm in diameter) to form a filter aidlayer (5 mm in thickness). The sample polymer solution was filtratedunder reduced pressure. Toluene in the filtrate was evaporated torecover the polymer.

Subsequently, as shown in Table 1, the oxygen concentration wascontrolled with a mixed gas composed of oxygen and nitrogen (oxygencontent: 6%). Then the heat treatment was repeated and the solid-liquidseparation was performed in the same way to recover the polymer.

Table 1 summarizes the molar ratio of charged oxygen atom [mol] tocopper [mol], the molar ratio of consumed oxygen atom [mol] to copper[mol] in the polymer, and the copper content, and result of the curingtest in the polymer.

TABLE 1 Oxygen Result of Curing Concentration Test Heating Internal [%]Charged Consumed Cu Content (Equivalents of Time Pressure Before AfterO/Cu O/Cu [ppm by Catalyst/Curing [h] [MPa] Heating Heating [mol/mol][mol/mol] weight] Time) 1 0.1 12.5 4.8 0.51 0.31 —  0.01/25 seconds 20.2 5.9 1.9 1.08 0.70 — 0.005/25 seconds 3 0.2 5.5 3 1.20 0.99 40.003/25 seconds 5 0.2 6.5 3.9 1.54 1.35 — 0.002/30 seconds 7 0.2 6.25.4 1.98 1.49 — 0.002/20 seconds

Comparative Example 3

Polymer solution [4] produced by Manufacturing Example 4 was dissolvedin the same weight of methylcyclohexane. The polymer solution (80 g) wascharged in a 100-mL autoclave (effective volumetric capacity: 170 mL).Adsorbents, i.e., a hydrotalcite adsorbent (2 parts by weight; Kyowaad500SH, Kyowa Chemical Industry Co., Ltd.) and aluminum silicate (2 partsby weight; Kyowaad 700SL, Kyowa Chemical Industry Co., Ltd.), were addedto the polymer solution containing 100 parts by weight of the polymer.The gas phase in the autoclave was completely replaced with nitrogen andthe autoclave was sealed. The temperature in the autoclave was increasedand the solution was heated at 150° C. for 2 hours. The mixture wassubjected to solid-liquid separation by ultracentrifugation (12,800 G,processing time: 2 minutes). Methylcyclohexane in the solution wasevaporated to recover the polymer. The copper content in the polymer was135 ppm by weight. According to the curing test of this polymer, whenthe content of the platinum catalyst was 0.045 equivalents, the curingtime was 35 seconds.

Manufacturing Example 5

In a 250-L reactor having a stirrer and a jacket, CuBr (923 g) wascharged and the atmosphere in the reactor was replaced with nitrogen.Acetonitrile (9.67 kg) was added, hot water was supplied through thejacket, and the mixture was stirred for 30 minutes at 80° C. Butylacrylate (110 kg) and diethyl 2,5-dibromoadipate (1.93 kg) were addedand the mixture was further stirred for 25 minutes at 80° C. Triamine(32.2 g) was added to the mixture to initiate the reaction. During thereaction, triamine (32.2 g) was further added four times to the mixture(128.8 g in total). After 6 hours from the initiation of the reaction,the atmosphere in the reactor was deaerated under reduced pressure at80° C. for 2 hours. 1,7-Octadiene (11.82 kg) and triamine (322 g) wereadded to the mixture and the mixture was stirred for 10 hours. Thus,Polymer solution [5] was recovered.

A small fraction of the polymer solution was sampled, and the samplesolution was diluted with three times the volume of toluene. The solidwas separated by filtration to recover a solution of a polymer havingterminal alkenyl groups (Polymer [5′]). The number average molecularweight of Polymer [5′] was 25,632, the molecular weight distribution ofPolymer [5′] was 1.28, and the average number of alkenyl groupsintroduced per one polymer molecule was 1.89.

Polymer solution [5] was heated under reduced pressure at 100° C. toevaporate acetonitrile and 1,7-octadiene to recover the polymer. Thecopper content in the polymer was 3,600 ppm by weight. The curing testwas performed using this polymer. Although 0.1 equivalents of theplatinum catalyst were added, the polymer was not cured within 3minutes.

EXAMPLE 6

Polymer [5′] produced by Manufacturing Example 5 was dissolved in thesame weight of methylcyclohexane. The polymer solution (80 g) wascharged in a 100-mL autoclave (effective volumetric capacity: 170 mL).Adsorbents, i.e., a hydrotalcite adsorbent (2 parts by weight; Kyowaad500SH, Kyowa Chemical Industry Co., Ltd.) and aluminum silicate (2 partsby weight; Kyowaad 700SL, Kyowa Chemical Industry Co., Ltd.), were addedto the polymer solution containing 100 parts by weight of the polymer.The gas phase in the autoclave was controlled with nitrogen so that theoxygen concentration was 10%. (The gas phase contained oxygen atoms of0.35 molar ratio to the copper content.) Then, the autoclave was sealed.The temperature in the autoclave was increased and the solution washeated at 150° C. for 2 hours. The solution was cooled to roomtemperature, and was subjected to solid-liquid separation byultracentrifugation (12,800 G, processing time: 2 minutes).Methylcyclohexane was evaporated to recover the polymer. The coppercontent in the polymer was 54 ppm by weight. According to the curingtest of this polymer, when the content of the platinum catalyst was0.025 equivalents, the curing time was 25 seconds.

Comparative Example 4

Polymer [5′] produced by Manufacturing Example 5 was dissolved in thesame weight of methylcyclohexane. The polymer solution (80 g) wascharged in a 100-mL autoclave (effective volumetric capacity: 170 mL).The gas phase (90 mL) in the autoclave was controlled with nitrogen sothat the oxygen content was 10%. (The gas phase contained oxygen atomsof 0.35 molar ratio to the copper content.) Then, the autoclave wassealed. The temperature in the autoclave was increased and the solutionwas heated at 150° C. for 2 hours. The solution was cooled to roomtemperature. A filter paper (4 μm) and a filter aid (Radiolite #700,Showa Chemical Industry Co., Ltd.) were disposed in a Kiriyama funnel(60 mm in diameter) to form a filter aid layer (5 mm in thickness). Thepolymer solution was filtrated under reduced pressure. Toluene in thefiltrate was evaporated to recover the polymer. The copper content inthe polymer was 121 ppm by weight. According to the curing test of thispolymer, when the content of the platinum catalyst was 0.07 equivalents,the curing time was 27 seconds.

According to the results of Example 6 and Comparative Example 4, in asystem without adsorbent, the heat treatment performed in anoxygen-containing atmosphere leads to remain a large amount of copper,i.e., a transition metal catalyst. Accordingly, a large amount of theplatinum catalyst was necessary, and the hydrosilylation activity of thepolymer was barely improved.

Comparative Example 5

A polymer was produced as in Example 6, but the gas phase in theautoclave was completely replaced with nitrogen. The copper content inthe polymer was 541 ppm by weight. The curing test was performed usingthis polymer. Although 0.1 equivalents of the platinum catalyst wereadded, the polymer was not cured within 3 minutes.

According to the results of Example 6 and Comparative Example 5, whenthe treatment with the adsorbent was performed in an oxygen-containingatmosphere, the hydrosilylation proceeded with smaller amount ofplatinum catalyst, compared with the treatment with the adsorbentperformed in nitrogen. Thus, the hydrosilylation activity of the polymerwas significantly improved.

Manufacturing Example 6

In a 2-L separable flask having a stirrer, CuBr (8.39 g) was charged andthe atmosphere in the reactor was replaced with nitrogen. Acetonitrile(87.92 g) was added and the temperature of the mixture was maintained at80° C. in a water bath. The mixture was stirred at 80° C. for 30minutes. Butyl acrylate (1,000 g) and diethyl 2,5-dibromoadipate (17.56g) were added, and the mixture was further stirred for 25 minutes at 80°C. Triamine (0.29 g) was added to the mixture to initiate the reaction.During the reaction, triamine (0.29 g) was further added four times tothe mixture (1.16 g in total). After 5 hours from the initiation of thereaction, the atmosphere in the reactor was deaerated under reducedpressure at 80° C. for 2 hours. 1,7-Octadiene (107.47 g) and triamine(2.9 g) were added to the mixture and the mixture was stirred for 4hours. Thus, Polymer solution [6] was recovered.

A small fraction of the polymer solution was sampled, and the samplesolution was diluted with three times the volume of toluene. The solidwas separated by filtration to recover a solution of a polymer havingterminal alkenyl groups (Polymer [6′]). The number average molecularweight of Polymer [6′] was 24,807, the molecular weight distribution ofPolymer [6′] was 1.24, and the average number of alkenyl groupsintroduced per one polymer molecule was 2.12.

EXAMPLE 7

Polymer solution [6] produced by Manufacturing Example 6 was heated at80° C. to evaporate acetonitrile and octadiene. Subsequently, thepolymer was dissolved in the same weight of toluene. The polymersolution (50 g) was charged in a 100-mL three-necked flask. While ahydrotalcite adsorbent (0.5 g; Kyowaad 500SH, Kyowa Chemical IndustryCo., Ltd.) and aluminum silicate (0.5 g; Kyowaad 700SL, Kyowa ChemicalIndustry Co., Ltd.) were adding to the solution, the mixture was heated.A reflux condenser was attached to the three-necked flask and a gasbagwas attached to the upper part in order to prevent vapor leakage. Whenthe temperature of the mixture went up to 80° C., the mixture wasmaintained at the temperature for 2 hours. Then the mixture was cooled.The mixture was subjected to solid-liquid separation byultracentrifugation (8,000 G, processing time: 2 minutes). Subsequentlytoluene was evaporated. According to the curing test of this polymer,when the content of the platinum catalyst was 0.008 equivalents, thecuring time was 30 seconds.

EXAMPLE 8

The polymer was purified as in Example 7, but the temperature of themixture was 100° C. According to the curing test of this polymer, whenthe content of the platinum catalyst was 0.006 equivalents, the curingtime was 32 seconds. Increasing the temperature provided a better resultcompared with Example 7.

EXAMPLE 9

The polymer was purified as in Examples 7 and 8, but the temperature ofthe mixture was 150° C. According to the curing test of this polymer,when the content of the platinum catalyst was 0.003 equivalents, thecuring time was 25 seconds. Increasing the temperature provided a betterresult compared with Example 8.

Manufacturing Example 7

In a 50-L reactor having a stirrer and a jacket, CuBr (251.3 g) wascharged and the atmosphere in the reactor was replaced with nitrogen.Acetonitrile (1.64 kg) was added, hot water was supplied through thejacket, and the mixture was stirred for 30 minutes at 80° C. Butylacrylate (30 kg) and diethyl 2,5-dibromoadipate (525 g) were added andthe mixture was further stirred for 25 minutes at 80° C. Triamine (12.22mL, 58.52 mmol) was added to the mixture to initiate the reaction.During the reaction, triamine (61.10 mL in total) was added to themixture. After 6 hours from the initiation of the reaction,1,7-octadiene (6.02 kg) and triamine (122.2 mL) were added to themixture and the mixture was stirred for 10 hours. Thus, Polymer solution[7] was recovered.

A small fraction of the polymer solution was sampled, and the samplesolution was diluted with three times the volume of toluene. The solidwas separated by filtration to recover a solution of a polymer havingterminal alkenyl groups (Polymer [7′]). The number average molecularweight of Polymer [7′] was 25,288, the molecular weight distribution ofPolymer [7′] was 1.23, and the average number of alkenyl groupsintroduced per one polymer molecule was 2.99.

EXAMPLE 10

Polymer solution [7] produced by Manufacturing Example 7 was evaporatedunder reduced pressure at 100° C. to remove acetonitrile and1,7-octadiene in Polymer solution [7]. Subsequently, the polymer wasdissolved in double the weight of toluene. The solid in the solution wasremoved with a disk centrifuge (LAPX 202, Alfa Laval K.K.) at 8,000 rpm.The liquid phase was condensed to recover the polymer. Subsequently, thepolymer was dissolved in the same weight of toluene. Furthermore,adsorbents, i.e., a hydrotalcite adsorbent (2 parts by weight; Kyowaad500SH, Kyowa Chemical Industry Co., Ltd.) and aluminum-silicate (2 partsby weight; Kyowaad 700SL, Kyowa Chemical Industry Co., Ltd.), were addedto the polymer solution containing 100 parts by weight of the polymer.The mixture was charged in a 100-mL autoclave, and stirred at 150° C.for 4 hours. Then the solution was left to cool to room temperature, andwas subjected to ultracentrifugation at 8,100 rpm for about 5 minutes.Toluene was removed from the resultant clear solution to recover thevinyl polymer. The residual copper content in the polymer was 40 ppm byweight.

EXAMPLE 11

Polymer solution [7] produced by Manufacturing Example 7 was evaporatedunder reduced pressure at 100° C. to remove acetonitrile and1,7-octadiene in Polymer solution [7]. Subsequently, the polymer wasdissolved in double the weight of toluene. The solid-liquid separationwas performed as in Example 10, and then the polymer was dissolved inthe same weight of toluene. Furthermore, adsorbents, i.e., ahydrotalcite adsorbent (1 part by weight; Kyowaad 500SH, Kyowa ChemicalIndustry Co., Ltd.) and aluminum silicate (1 part by weight; Kyowaad700SL, Kyowa Chemical Industry Co., Ltd.), were added to the polymersolution contaianing 100 parts by weight of the polymer. The mixture wascharged in a 100-mL autoclave, and was stirred at 150° C. for 4 hours.Then the solution was left to cool to room temperature, and wassubjected to ultracentrifugation at 8,100 rpm for about 5 minutes.Toluene was removed from the resultant clear solution to recover thevinyl polymer. The residual copper content in the polymer was 35 ppm byweight.

Comparative Example 6

Polymer solution [7] produced by Manufacturing Example 7 was evaporatedunder reduced pressure at 100° C. to remove acetonitrile and1,7-octadiene in Polymer solution [7]. The solid-liquid separation wasperformed as in Example 10. Subsequently, the polymer was dissolved inthe same weight of toluene. The solution was charged in a 100-mLautoclave, and was stirred at 150° C. for 4 hours. Then the solution wasleft to cool to room temperature, and was subjected toultracentrifugation at 8,100 rpm for about 5 minutes. Toluene wasremoved from the resultant clear solution to recover the vinyl polymer.The residual copper content in the polymer was 462 ppm by weight.

According to the results of Examples 10, 11 and Comparative Example 6,in a system without adsorbent, the heat treatment performed in anoxygen-containing atmosphere leads to remain a large amount of copper,i.e., a transition metal catalyst.

EXAMPLE 12

Polymer solution [7] produced by Manufacturing Example 7 was evaporatedunder reduced pressure at 100° C. to remove acetonitrile and1,7-octadiene in Polymer solution [7]. Subsequently, the polymer wasdissolved in double the weight of toluene. The solid-liquid separationwas performed as in Example 10. Subsequently, the polymer was dissolvedin the same weight of methylcyclohexane. Furthermore, adsorbents, i.e.,a hydrotalcite adsorbent (2 parts by weight; Kyowaad 500SH, KyowaChemical Industry Co., Ltd.) and aluminum silicate (2 parts by weight;Kyowaad 700SL, Kyowa Chemical Industry Co., Ltd.) were added to thepolymer solution containing 100 parts by weight of the polymer. Themixture was charged in a 100-mL autoclave, and was stirred at 150° C.for 4 hours. Then the solution was left to cool to room temperature, andwas subjected to ultracentrifugation at 8,100 rpm for about 5 minutes.Toluene was removed from the resultant clear solution to recover thevinyl polymer. The residual copper content in the polymer was less than10 ppm by weight.

Table 2 summarizes the results (the copper content in polymers havingalkenyl groups, equivalents of the catalyst used in the curing tests ofthe polymers having alkenyl groups, and curing times in the curing testswith the equivalents of the catalyst) of the purified polymers andunpurified polymers in the above Examples and Comparative Examples.

TABLE 2 Cu Curing [ppm by Equivalents Time Polymer Solvent TemperatureAdsorbent Oxygen weight of Catalyst (sec.) Example 1 ManufacturingExample 1 Not Used 150° C. Used Used — 0.0007 30 Example 2 ManufacturingExample 2 Not Used 130° C. Used Used 21 0.0006 29 Example 3Manufacturing Example 3 Not Used 130° C. Used Used <2 0.0003 20 Example4 Manufacturing Example 4 Not Used 150° C. Used Used <2 0.0007 36Example 5 Manufacturing Example 4 Methylcyclohexane 150° C. Used Used 40.003 25 Example 6 Manufacturing Example 5 Methylcyclohexane 150° C.Used Used 54 0.025 25 Example 7 Manufacturing Example 6 Toluene  80° C.Used Used — 0.008 30 Example 8 Manufacturing Example 6 Toluene 100° C.Used Used — 0.006 32 Example 9 Manufacturing Example 6 Toluene 150° C.Used Used — 0.003 25 Example 10 Manufacturing Example 7 Toluene 150° C.Used Used 40 — — Example 11 Manufacturing Example 7 Toluene 150° C. UsedUsed 35 — — Example 12 Manufacturing Example 7 Methylcyclohexane 150° C.Used Used <10 — — Comparative Manufacturing Example 2 Not Used 130° C.Used Not 16 0.002 35 Example 1 used Comparative Manufacturing Example 4Not Used 150° C. Used Not <2 0.003 36 Example 2 used ComparativeManufacturing Example 4 Methylcyclohexane 150° C. Used Not 135 0.045 35Example 3 Used Comparative Manufacturing Example 5 Methylcyclohexane150° C. Not Used Used 121 0.07 27 Example 4 Comparative ManufacturingExample 5 Methylcyclohexane 150° C. Used Not 541 0.1 Not Example 5 UsedCured Comparative Manufacturing Example 7 Toluene 150° C. Not Used Used462 — — Example 6

EXAMPLE 13

Synthesis and Purification of Poly (n-butyl acrylate) Having OneTerminal Bromo Group

In a reactor having a stirrer, CuBr (4.2 parts by weight) andacetonitrile (44.0 parts by weight) were charged, and the mixture wasstirred at 70° C. for 15 minutes in nitrogen. Butyl acrylate (100 partsby weight) and ethyl 2-bromobutyrate (9.5 parts by weight) were added,and the mixture was stirred sufficiently. Triamine (0.17 parts byweight) was added to the mixture to initiate the reaction. While themixture was stirring at 80° C., butyl acrylate (400 parts by weight) wasadded dropwise continuously. During adding the acrylic ester dropwise,triamine (0.68 parts by weight in total) was further added several timesto the mixture. When the conversion reached 96%, acetonitrile containingthe residual monomer was evaporated at 80° C. to recover poly (n-butylacrylate) having one terminal bromo group, i.e., having one terminalbromo group at one end of the polymer (hereinafter referred to asPolymer [8]). The number average molecular weight of Polymer [8] was11,800 and the molecular weight distribution of Polymer [8] was 1.08.

A filter aid (2 parts by weight; zeolite R900, Showa Chemical IndustryCo., Ltd.) and methylcyclohexane (100 parts by weight) were added toPolymer [8] (100 parts by weight). The mixture was stirred at 80° C. innitrogen. The solid in the mixture was filtrated to prepare a solutionof methylcyclohexane containing Polymer [8]. The copper content of thepolymer was 59 ppm by weight.

Adsorbents (4 parts by weight in total), i.e., a hydrotalcite adsorbent(2 parts by weight; Kyowaad 500SH, Kyowa Chemical Industry Co., Ltd.)and aluminum silicate (2 parts by weight; Kyowaad 700SL, Kyowa ChemicalIndustry Co., Ltd.), were added to the solution of methylcyclohexanecontaining 100 parts by weight of Polymer [8]. The mixture was stirredat 80° C. for 2 hours in a mixed gas containing oxygen and nitrogen(oxygen content: 6%). The insoluble was removed and the polymer solutionwas condensed to recover a polymer having one terminal group (Polymer[8′]). The number average molecular weight of Polymer [8′] was 11,800and the molecular weight distribution of Polymer [8′] was 1.08. Thecopper content in the polymer was 2 ppm by weight or less.

EXAMPLE 14

Synthesis and Purification of Poly (n-butyl acrylate) having TwoTerminal Bromo Groups

In a reactor having a stirrer, CuBr (4.2 parts by weight) andacetonitrile (44.0 parts by weight) were charged, and the mixture wasstirred at 70° C. for 15 minutes in nitrogen. Butyl acrylate (100 partsby weight) and diethyl 2,5-dibromoadipate (8.8 parts by weight) wereadded, and the mixture was stirred sufficiently. Triamine (0.17 parts byweight) was added to the mixture to initiate the reaction. While themixture was stirring at 80° C., butyl acrylate (400 parts by weight) wasadded dropwise continuously. During adding the butyl acrylate dropwise,triamine (0.85 parts by weight in total) was further added several timesto the mixture. When the monomer conversion reached 97%, acetonitrilecontaining the residual monomer was evaporated at 80° C. to recover poly(n-butyl acrylate) having two terminal bromo groups, i.e., havingterminal bromo groups at both ends of the polymer (hereinafter referredto as Polymer [9]). The number average molecular weight of Polymer [9]was 24,200 and the molecular weight distribution of Polymer [9] was1.23.

Polymer [9] (100 parts by weight) was diluted with methylcyclohexane(100 parts by weight). The solid in the mixture was filtrated to preparea solution of Polymer [9].

Adsorbents (10 parts by weight in total), i.e., a hydrotalcite adsorbent(5 parts by weight;.Kyowaad 500SH, Kyowa Chemical Industry Co., Ltd.)and aluminum silicate (5 parts by weight; Kyowaad 700SL, Kyowa ChemicalIndustry Co., Ltd.), were added to the solution of methylcyclohexanecontaining 100 parts by weight of Polymer [9]. The mixture was stirredat 80° C. for 2 hours in a mixed gas containing oxygen and nitrogen(oxygen content: 21%). The insoluble was removed in an open system in alaboratory, and the polymer solution was condensed to recover a polymerhaving two terminal bromo groups (Polymer [9′]). The number averagemolecular weight of Polymer [9′] was 24,500 and the molecular weightdistribution of Polymer [9′] was 1.20. The copper content in the polymerwas 2 ppm by weight or less.

EXAMPLE 15

Synthesis and Purification of Poly (n-butyl acrylate) having OneTerminal Hydroxyl Group

In a 50-L pressure reactor, cuprous bromide (251.82 g, 1.76 mol),acetonitrile (2.64 kg), butyl acrylate (33.6 L, 30 kg, 234 mol), diethyl2,5-dibromoadipate (527 g, 1.46 mol), and pentamethyldiethylenetriamine(12.2 mL, 10.1 g, 58.5 mmol) were charged under nitrogen atmosphere, andthe mixture was stirred at 70° C. for 150 minutes. According to gaschromatography, the consumption rate of the butyl acrylate was 98%. Thenthe mixture was heated under reduced pressure to remove volatilecomponents. Acetonitrile (3.96 kg) and 5-hexenol (3.51 L, 2.93 kg, 29.3mol) were added to the mixture and the mixture was further stirred at80° C. for 8 hours. The mixture was heated under reduced pressure toremove volatile components to recover a polymer having a terminalhydroxyl group, i.e., having one terminal hydroxyl group at one end ofthe polymer (Polymer [10]). The number average molecular weight ofPolymer [10] was 26,200 and the molecular weight distribution of Polymer[10] was 1.27. The introducing rate of hydroxyl group based on thenumber average molecular weight was 2.0.

Polymer [10] (100 parts by weight) was diluted with methylcyclohexane(100 parts by weight). The solid in the mixture was filtrated to preparea solution of Polymer [10].

Adsorbents (10 parts by weight in total), i.e., a hydrotalcite adsorbent(5 parts by weight; Kyowaad 500SH, Kyowa Chemical Industry Co., Ltd.)and aluminum silicate (5 parts by weight; Kyowaad 700SL, Kyowa ChemicalIndustry Co., Ltd.), were added to the solution of methylcyclohexanecontaining 100 parts by weight of Polymer [10]. The mixture was stirredat 100° C. for 4 hours in a mixed gas containing oxygen and nitrogen(oxygen content: 6%). Solid-liquid separation was performed with a bagfilter, and the polymer solution was condensed to recover a polymerhaving one terminal hydroxyl group (Polymer [10′]). The number averagemolecular weight of Polymer [10′] was 26,900 and the molecular weightdistribution of Polymer [10′] was 1.30. The copper content in thepolymer was 2 ppm by weight or less. The average number of hydroxylgroups per one polymer molecule was 2.1.

INDUSTRIAL APPLICABILITY

Since the present invention is constituted as described above, thepresent invention can provide a simple, economical, and efficient methodfor improving the hydrosilylation activity of a vinyl polymer withmaintaining the original properties of the vinyl polymer. Thus, thevinyl polymer can be preferably used as a component of a reactivecomposition susceptible to hydrosilylation; furthermore, the amount ofthe adsorbent in use can be decreased.

1. A method for producing a vinyl polymer, comprising the steps of:polymerizing a vinyl monomer by atom transfer radical polymerizationwith a transition metal complex as a polymerization catalyst; andbringing the resultant vinyl polymer into contact with an adsorbent inthe presence of an oxidizing agent, wherein the oxidizing agentcomprises oxygen molecules, the oxidizing agent being a mixed gascomprising oxygen and nitrogen, the oxygen atom content in the mixed gasbeing 0.1 to 5,000 molar ratio to the total transition metal in thereaction system.
 2. A method for producing a vinyl polymer, comprisingthe steps of: polymerizing a vinyl monomer by atom transfer radicalpolymerization with a transition metal complex as a polymerizationcatalyst; and bringing the resultant vinyl polymer into contact with anadsorbent in the presence of an oxidizing agent, wherein the oxidizingagent comprises hydrogen peroxide, the oxygen atom content in thehydrogen peroxide being 0.1 to 100 molar ratio to the total transitionmetal in the reaction system.
 3. The method according to claim 1,wherein the oxidizing agent further comprises sodium percarbonate, theoxygen atom content in the sodium percarbonate being 0.1 to 100 molarratio to the total transition metal in the reaction system.
 4. Themethod according to claim 1, wherein the adsorbent is an inorganicadsorbent or an activated carbon.
 5. The method according to claim 1,wherein the adsorbent is at least one selected from the group consistingof magnesium oxide, activated clay, aluminum silicate, activatedalumina, and hydrotalcite compounds.
 6. The method according to claim 1,wherein the step of bringing the vinyl polymer into contact with theadsorbent in the presence of the oxidizing agent is performed in asolvent-free system.
 7. The method according to claim 1, wherein thestep of bringing the vinyl polymer into contact with the adsorbent isperformed at 20° C. to 250° C. in the presence of the oxidizing agentand a solvent, and the adsorbent is separated from the vinyl polymer bycentrifugation, plain sedimentation, or filtration.
 8. The methodaccording to claim 7, wherein the step of bringing the vinyl polymerinto contact with the adsorbent is performed at 80° C. to 250° C. in thepresence of the oxidizing agent and the solvent.
 9. The method accordingto claim 7, wherein the solvent has a relative dielectric constant of 5or less at 25° C.
 10. The method according to claim 7, wherein thesolvent comprises at least one selected from the group consisting ofn-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, toluene,xylenes, butyl acetate, and diethyl ether.
 11. The method according toclaim 1, wherein the step of polymerizing the vinyl monomer by atomtransfer radical polymerization with the transition metal complex as thepolymerization catalyst is performed in the presence of a polymerizationsolvent, the polymerization solvent is removed, and the resultant vinylpolymer is brought into contact with the adsorbent in the presence ofthe oxidizing agent.
 12. The method according to claim 1, wherein thestep of polymerizing the vinyl monomer by atom transfer radicalpolymerization with the transition metal complex as the polymerizationcatalyst is performed, the resultant vinyl polymer is brought intocontact with the adsorbent in the presence of the oxidizing agent and asolvent, and the resultant vinyl polymer is brought into contact withthe adsorbent in the presence of the oxidizing agent in a solvent-freesystem.
 13. A method for producing a vinyl polymer, comprising the stepsof: polymerizing a vinyl monomer by atom transfer radical polymerizationwith a transition metal complex as a polymerization catalyst; andbringing the resultant vinyl polymer into contact with an adsorbent inthe presence of an oxidizing agent, wherein the step of bringing theresultant vinyl polymer into contact with the adsorbent is performed inthe presence of water, the content of the water being 0.1 to 1,000 molarratio to the total transition metal in the reaction system.
 14. Themethod according to claim 1, wherein the central metal of the transitionmetal complex is an element in group 8, group 7, group 10, or group 11in the periodic table.
 15. The method according to claim 14, wherein thecentral metal of the transition metal complex is iron, nickel,ruthenium, or copper.
 16. The method according to claim 14, wherein thecentral metal of the transition metal complex is copper.
 17. The methodaccording to claim 1, wherein the transition metal complex is preparedfrom CuBr.
 18. The method according to claim 1, wherein the transitionmetal complex includes a polyamine ligand.
 19. The method according toclaim 1, wherein the transition metal complex includes a triamineligand.
 20. The method according to claim 1, wherein the vinyl polymerhas at least one alkenyl group per molecule.
 21. The method according toclaim 20, wherein the alkenyl groups reside at terminals of themolecular chain of the vinyl polymer.
 22. The method according to claim20, wherein the vinyl polymer having alkenyl groups is produced byadding a compound having at least two carbon-carbon double bonds havinglow polymerizability, the compound being added during or after thepolymerization in atom transfer radical polymerization.
 23. The methodaccording to claim 1, wherein the vinyl polymer has at least one bromineatom per molecule.
 24. The method according to claim 1, wherein thevinyl polymer has at least one hydroxyl group per molecule.
 25. Themethod according to claim 2, wherein the adsorbent is an inorganicadsorbent or an activated carbon.
 26. The method according to claim 2,wherein the adsorbent is at least one selected from the group consistingof magnesium oxide, activated clay, aluminum silicate, activatedalumina, and hydrotalcite compounds.
 27. The method according to claim2, wherein the step of bringing the vinyl polymer into contact with theadsorbent in the presence of the oxidizing agent is performed in asolvent-free system.
 28. The method according to claim 2, wherein thestep of bringing the vinyl polymer into contact with the adsorbent isperformed at 20° C. to 250° C. in the presence of the oxidizing agentand a solvent, and the adsorbent is separated from the vinyl polymer bycentrifugation, plain sedimentation, or filtration.
 29. The methodaccording to claim 28, wherein the step of bringing the vinyl polymerinto contact with the adsorbent is performed at 80° C. to 250° C. in thepresence of the oxidizing agent and the solvent.
 30. The methodaccording to claim 28, wherein the solvent has a relative dielectricconstant of 5 or less at 25° C.
 31. The method according to claim 28,wherein the solvent comprises at least one selected from the groupconsisting of n-hexane, cyclohexane, methylcyclohexane,ethylcyclohexane, toluene, xylenes, butyl acetate, and diethyl ether.32. The method according to claim 2, wherein the step of polymerizingthe vinyl monomer by atom transfer radical polymerization with thetransition metal complex as the polymerization catalyst is performed inthe presence of a polymerization solvent, the polymerization solvent isremoved, and the resultant vinyl polymer is brought into contact withthe adsorbent in the presence of the oxidizing agent.
 33. The methodaccording to claim 2, wherein the step of polymerizing the vinyl monomerby atom transfer radical polymerization with the transition metalcomplex as the polymerization catalyst is performed, the resultant vinylpolymer is brought into contact with the adsorbent in the presence ofthe oxidizing agent and a solvent, and the resultant vinyl polymer isbrought into contact with the adsorbent in the presence of the oxidizingagent in a solvent-free system.
 34. The method according to claim 2,wherein the central metal of the transition metal complex is an elementin group 8, group 7, group 10, or group 11 in the periodic table. 35.The method according to claim 34, wherein the central metal of thetransition metal complex is iron, nickel, ruthenium, or copper.
 36. Themethod according to claim 34, wherein the central metal of thetransition metal complex is copper.
 37. The method according to claim 2,wherein the transition metal complex is prepared from CuBr.
 38. Themethod according to claim 2, wherein the transition metal complexincludes a polyamine ligand.
 39. The method according to claim 2,wherein the transition metal complex includes a triamine ligand.
 40. Themethod according to claim 2, wherein the vinyl polymer has at least onealkenyl group per molecule.
 41. The method according to claim 40,wherein the alkenyl groups reside at terminals of the molecular chain ofthe vinyl polymer.
 42. The method according to claim 40, wherein thevinyl polymer having alkenyl groups is produced by adding a compoundhaving at least two carbon-carbon double bonds having lowpolymerizability, the compound being added during or after thepolymerization in atom transfer radical polymerization.
 43. The methodaccording to claim 2, wherein the vinyl polymer has at least one bromineatom per molecule.
 44. The method according to claim 2, wherein thevinyl polymer has at least one hydroxyl group per molecule.